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

Abstract

To provide a photosensitive resin composition having a low coefficient of thermal expansion, excellent adhesion to a metal film and improved reliability.SOLUTION: Provided are a photosensitive resin composition including (A) a resin, (B) a photopolymerizable compound including a compound represented by the following Chemical Formula 1, (C) a photopolymerization initiator, and (D) a solvent, a photosensitive resin film prepared by using the same, and a semiconductor device including the photosensitive resin film. Wherein R1 and R2 are independently hydrogen or a substituted or unsubstituted C1 -C20 alkyl group; and L1 -L3 are independently a substituted or unsubstituted C1 -C20 alkylene group, a substituted or unsubstituted C3 -C20 cycloalkylene group, a substituted or unsubstituted C6 -C20 arylene group, or a combination thereof SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive resin film using the same, and a semiconductor device. [Background technology]

[0002] A commercially available method is to encapsulate semiconductor devices with epoxy resin compositions to protect them from external environmental factors such as moisture and mechanical shock. Conventionally, semiconductor devices were encapsulated by dicing wafers to produce semiconductor chips, which were then packaged individually. However, recently, a new process has been developed in which semiconductor chips are packaged in an undiced wafer or larger panel state and then diced. The former process is generally called chip scale packaging (CSP), while the latter process is called wafer level packaging (WLP) or panel level packaging (PLP).

[0003] Wafer-level packaging (WLP) offers advantages over chip-scale packaging (CSP), including higher process yields, smaller package thickness, and reduced semiconductor packaging space. However, because wafer-level packaging and panel-level packaging require a larger deposition area than chip-scale packaging, which seals individual chips, they can suffer from significant warpage due to the difference in thermal expansion coefficients between the wafer or panel and the encapsulant. Warpage can affect the yield of subsequent processes and wafer handling. Additionally, liquid epoxy resins or silicone resins are currently used as encapsulants in WLP and PLP. However, these liquid compositions often contain low inorganic fillers and use liquid monomolecular resins, which can result in poor reliability of the sealed semiconductor package.

[0004] Therefore, there is a need to develop an insulating film for a redistribution layer (RDL) that has low warpage and excellent reliability even when applied to wafer level packaging or panel level packaging.

[0005] To meet this demand, development of photosensitive resin compositions capable of forming insulating films for redistribution layers has been ongoing. Generally, photosensitive polyimide resin compositions, in which the polyimide resin itself is photosensitive, have been primarily used. This is because the use of photosensitive polyimide resin compositions simplifies the pattern formation process. However, insulating films (cured films) for redistribution layers manufactured using conventional photosensitive polyimide resin compositions suffer from the problem of reduced corrosion resistance and chemical resistance. In particular, resins for insulating films for redistribution layers require low-temperature curing, but conventional photosensitive polyimide resins are unable to achieve low-temperature curing, resulting in the problem of being unable to achieve high heat resistance and high reliability. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of one embodiment is to provide a photosensitive resin composition that uses a compound having a specific structure as an additive, and that has a low thermal expansion coefficient, excellent adhesion to a metal film, and improved reliability.

[0007] Another embodiment of the present invention provides a photosensitive resin film produced using the photosensitive resin composition.

[0008] Another object of another embodiment is to provide a semiconductor element including this photosensitive resin film. [Means for solving the problem]

[0009] One embodiment is a photosensitive resin composition comprising (A) a resin, (B) a photopolymerizable compound including a compound represented by the following chemical formula 1, (C) a photopolymerization initiator, and (D) a solvent.

[0010] [ka]

[0011] In formula 1, R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 ~L 3 are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0012] In formula 1, R 1 and R 2 may each independently be a methyl group.

[0013] In chemical formula 1, L 2 and L 3 may each independently be an unsubstituted C1 to C20 alkylene group.

[0014] In chemical formula 1, L 1 can be represented by the following chemical formula L.

[0015] [ka]

[0016] In the chemical formula L, R 3 ~R 6 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, provided that R 3 and R 5 At least one of R is a substituted or unsubstituted C1 to C20 alkyl group, 4 and R 6 At least one of L is a substituted or unsubstituted C1 to C20 alkyl group. 4 ~L 6are each independently an unsubstituted C1 to C20 alkylene group.

[0017] In the chemical formula L, L 5 and L 6 may be different from each other.

[0018] The compound represented by Chemical Formula 1 may have an asymmetric structure.

[0019] The resin may be a polyamic acid or polyamic ester resin containing a structural unit represented by the following chemical formula 2.

[0020] [ka]

[0021] In chemical formula 2, X 1 is a residue derived from a monoanhydride or dianhydride monomer, and Y 1 is a residue derived from a diamine monomer, and R 7 and R 8 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

[0022] The monoanhydride monomer or dianhydride monomer can be represented by the following chemical formula 2-1 or 2-2.

[0023] [ka]

[0024] In chemical formula 2-1, L 7 is a single bond, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-C(=O)O-*, *-NR 0 -*(R 0is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic linking group, or a combination thereof.

[0025] The resin can include residues derived from a monoanhydride monomer represented by formula 2-2.

[0026] The diamine monomer can be represented by the following Chemical Formula 2-3 or Chemical Formula 2-4.

[0027] [ka]

[0028] In Chemical Formula 2-3 and Chemical Formula 2-4, R 11 and R 12 are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and m1 and m2 are each independently an integer of 0 to 4.

[0029] The above-mentioned photopolymerizable compound may further include a compound having a structure different from that of the compound represented by Chemical Formula 1.

[0030] The photosensitive resin composition may contain 1 to 30 parts by weight of a photopolymerizable compound, 1 to 10 parts by weight of a photopolymerization initiator, and 100 to 500 parts by weight of a solvent, relative to 100 parts by weight of resin.

[0031] The photosensitive resin composition may further contain additives such as diacids, alkanolamines, leveling agents, silane coupling agents, surfactants, epoxy compounds, thermal latent acid generators, or combinations thereof.

[0032] The photosensitive resin composition may be a negative photosensitive resin composition.

[0033] Another embodiment is a photosensitive resin film produced using the photosensitive resin composition.

[0034] The photosensitive resin film may be a semiconductor rewiring layer insulating film.

[0035] Yet another embodiment is a semiconductor element including a photosensitive resin film.

[0036] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0037] The photosensitive resin composition according to one embodiment contains a compound having a specific structure as an additive, which improves adhesion to metal layers (e.g., copper layers, silicon layers, titanium layers, etc.) and reduces the thermal expansion coefficient, thereby realizing an insulating film for a semiconductor redistribution layer with excellent reliability. [Brief explanation of the drawings]

[0038] [Figure 1] FIG. 1 is a schematic diagram of a die shear tester device for evaluating the adhesive strength of a photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0039] DETAILED DESCRIPTION OF THE INVENTION The following detailed description of the present invention is provided by way of example only, and is not intended to limit the scope of the present invention, which is defined solely by the scope of the claims that follow.

[0040] Unless otherwise specified in this specification, an "alkyl group" means a C1 to C20 alkyl group, an "alkenyl group" means a C2 to C20 alkenyl group, a "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, a "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, an "aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C7 to C20 arylalkyl group, an "alkylene group" means a C1 to C20 alkylene group, an "arylene group" means a C6 to C20 arylene group, an "alkylarylene group" means a C7 to C20 alkylarylene group, a "heteroarylene group" means a C3 to C20 heteroarylene group, and an "alkoxyylene group" means a C1 to C20 alkoxyylene group.

[0041] Unless otherwise specified in this specification, "substituted" means a C1 to C20 alkyl group in which at least one hydrogen atom has been substituted with a halogen atom (F, Cl, Br, I), a halogen atom such as a trifluoromethyl group, a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group, or means substituted with a substituent group selected from the group consisting of 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.

[0042] Unless otherwise specified in this specification, the term "hetero" means that at least one heteroatom selected from N, O, S, and P is contained in the chemical formula.

[0043] In addition, unless otherwise specified, "(meth)acrylate" in this specification means both "acrylate" and "methacrylate."

[0044] Unless otherwise defined herein, "combination" means blending or copolymerization, "copolymerization" means block copolymerization, alternating copolymerization, or random copolymerization, and "copolymer" means block copolymerization, alternating copolymerization, or random copolymerization.

[0045] Unless otherwise specified in this specification, unsaturated bonds include not only multiple bonds between carbon atoms, but also bonds containing other molecules such as carbonyl bonds, azo bonds, and the like.

[0046] Unless otherwise defined in the chemical formulas herein, when no chemical bond is drawn at a position where a chemical bond should be drawn, this means that a hydrogen atom is bonded at that position.

[0047] Unless otherwise defined herein, "*" refers to a position connected to the same or different atom or chemical formula.

[0048] A photosensitive resin composition according to one embodiment includes (A) a resin, (B) a photopolymerizable compound including a compound represented by the following Chemical Formula 1, (C) a photopolymerization initiator, and (D) a solvent.

[0049] [ka]

[0050] In formula 1, R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 ~L 3 are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0051] Each component will be specifically described below.

[0052] (A) Resin The resin used in the photosensitive resin composition according to one embodiment may be a polyamic acid or polyamic ester-based resin, and the polyamic acid or polyamic ester-based resin may include a structural unit represented by the following Chemical Formula 2:

[0053] [ka]

[0054] In chemical formula 2, X 1 is a residue derived from a monoanhydride or dianhydride monomer, and Y 1 is a residue derived from a diamine monomer, and R 7 and R 8 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group. For example, R 7 and R 8 may each independently be a C1 to C20 alkyl group that is unsubstituted or substituted with a (meth)acrylate group.

[0055] When used in combination with the compound represented by Chemical Formula 1, polyamic acid or polyamic ester resins containing the structural unit represented by Chemical Formula 2 can maintain low sensitivity without scumming in the underlying film. Furthermore, they can reduce the coefficient of thermal expansion (CTE) and improve adhesion to metal layers. Furthermore, they can be easily applied to negative-tone compositions to significantly improve developability.

[0056] Generally, resins having a closed ring structure have the problem of slightly deteriorating film properties when cured at low temperatures. However, since the polyamic acid or polyamic ester resin containing the structural unit represented by Chemical Formula 2 is used together with the compound represented by Chemical Formula 1, the photosensitive resin composition according to one embodiment is suitable for low temperature curing and can provide an insulating film (cured film) with excellent film properties.

[0057] In particular, in light of the recent trend toward multi-layered redistribution layers, the photosensitive resin composition according to one embodiment is in line with the recent trend in that it can bring the CTE of the copper metal of the redistribution layer closer to that of the insulating film material of the redistribution layer, thereby improving the crack and delamination rates in reliability test environments.

[0058] For example, the polyamic acid or polyamic ester resin containing the structural unit represented by Chemical Formula 2 may be a polymer of a "monoanhydride monomer or dianhydride monomer" and a "diamine monomer."

[0059] For example, the diamine monomer may be represented by the following Formula 2-3 or Formula 2-4.

[0060] [ka]

[0061] In Chemical Formula 2-3 and Chemical Formula 2-4, R 11 and R 12 are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and m1 and m2 are each independently an integer of 0 to 4.

[0062] For example, the monoanhydride monomer or dianhydride monomer may include, but is not necessarily limited to, a monomer represented by the following Formula 2-1 or Formula 2-2:

[0063] [ka]

[0064] In chemical formula 2-1, L 7 is a single bond, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-C(=O)O-*, *-NR 0 -*(R 0 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic linking group, or a combination thereof.

[0065] For example, L 7 When is a substituted or unsubstituted C1 to C20 alkylene group, it may be a C1 to C20 alkylene group substituted or unsubstituted with a trifluoroalkyl group.

[0066] For example, the resin may contain a residue derived from the monoanhydride monomer represented by Chemical Formula 2-2. In this case, the resin is advantageous in terms of sensitivity, thermal expansion coefficient, and adhesive strength compared to a resin that does not contain a residue derived from the monoanhydride monomer represented by Chemical Formula 2-2.

[0067] For example, in formula 2, X 1 is a residue derived from a monoanhydride monomer represented by formula 2-2 or a dianhydride monomer represented by formula 2-1 (where L 7 is not a single bond), and a residue derived from a monoanhydride monomer represented by formula 2-2. 1 is a dianhydride monomer represented by chemical formula 2-1 (where L 7is not a single bond) and a residue derived from a monoanhydride monomer represented by formula 2-2, a dianhydride monomer represented by formula 2-1 (where L 7 is not a single bond) may be equal to or greater than the number of moles of the residue derived from the monoanhydride monomer represented by Chemical Formula 2-2. This is advantageous in terms of sensitivity, thermal expansion coefficient, and adhesive strength, and in particular, the thermal expansion coefficient can be significantly reduced.

[0068] Weight average molecular weight (M w ) may be 3,000 g / mol to 300,000 g / mol. When the weight average molecular weight of the polyamic acid or polyamic ester resin is within the above range, sufficient physical properties can be obtained, the resin has excellent solubility in organic solvents, and is easy to handle.

[0069] (B) Photopolymerizable compound The photopolymerizable compound in the photosensitive resin composition according to one embodiment includes a compound represented by Chemical Formula 1.

[0070] When the compound represented by Chemical Formula 1 is contained, it can be used together with the above-mentioned resins to form a photosensitive resin composition that is advantageous for low-temperature curing, and can also improve scum characteristics, sensitivity, thermal expansion coefficient, and adhesive strength, making it very suitable for use as an insulating film between semiconductor redistribution layers.

[0071] The compound represented by Chemical Formula 1 has (meth)acrylate groups at both ends connected to each other by an intermediate linking group, and an additional urethane linking group between the (meth)acrylate group and the intermediate linking group. This structure reduces the coefficient of thermal expansion when mixed with a resin, specifically a polyamic acid or polyamic ester resin, and can improve sensitivity and even adhesion, making the photosensitive resin composition according to one embodiment highly advantageous for use as an insulating film for a semiconductor redistribution layer.

[0072] For example, in Formula 1, R 1 and R 2 may each independently be a methyl group. That is, the compound represented by Chemical Formula 1 may contain methacrylate groups at both ends.

[0073] For example, in Formula 1, L 2 and L 3 may each independently be an unsubstituted C1 to C20 alkylene group, but is not necessarily limited to this.

[0074] For example, in Formula 1, L 1 can be represented by the following chemical formula L.

[0075] [ka]

[0076] In the chemical formula L, R 3 ~R 6 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, provided that R 3 and R 5 At least one of R is a substituted or unsubstituted C1 to C20 alkyl group, 4 and R 6 At least one of L is a substituted or unsubstituted C1 to C20 alkyl group. 4 ~L 6 are each independently an unsubstituted C1 to C20 alkylene group.

[0077] For example, in the chemical formula L, L 5 and L 6 may be different from each other. For example, the compound represented by Chemical Formula 1 may have an asymmetric structure.

[0078] By having a linking group such as that of chemical formula L as an intermediate linking group, it becomes easy to simultaneously improve the sensitivity, thermal expansion coefficient, and adhesive strength, and these effects are more easily achieved when the compound represented by chemical formula 1 has an asymmetric structure than when it has a symmetric structure.

[0079] Specifically, the compound represented by Chemical Formula 1 may be a single compound or a mixture of two or more compounds within the scope of Chemical Formula 1. For example, if the compound represented by Chemical Formula 1 exists in the form of a mixture of two compounds, the mixture may contain these two compounds in a weight ratio of 50:50.

[0080] The compound represented by Chemical Formula 1 may be contained in an amount of 1 to 10 parts by weight, for example, 1 to 5 parts by weight, relative to 100 parts by weight of the resin. When the compound represented by Chemical Formula 1 is contained in the above range, the adhesive strength to the resin is improved, and at the same time, the sensitivity and adhesive strength properties can also be improved.

[0081] For example, the photopolymerizable compound may further include a compound having a structure different from that of the compound represented by Chemical Formula 1. In this case, the compound represented by Chemical Formula 1 may be included in an amount less by weight than the compound having the structure different from that of the compound represented by Chemical Formula 1.

[0082] For example, a compound having a structure different from that of the compound represented by Chemical Formula 1 can be represented by Chemical Formula 6 below.

[0083] [ka]

[0084] In Chemical Formula 6, t is an integer of 1 to 10, for example, an integer of 5 to 10.

[0085] For example, the compound represented by Chemical Formula 6 may be contained in an amount of 10 to 20 parts by weight, e.g., 10 to 15 parts by weight, relative to 100 parts by weight of the resin. When the compound represented by Chemical Formula 6 is contained within the above range, the effect of improving the adhesive strength to the resin and the sensitivity can be further enhanced.

[0086] Meanwhile, the photopolymerizable compound may further include a compound having at least two functional groups represented by the following Chemical Formula 3.

[0087] [ka]

[0088] In formula 3, R 100 is a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group, and L 100 is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

[0089] For example, a compound containing at least two functional groups represented by Chemical Formula 3 can contain 2 to 6 functional groups represented by Chemical Formula 3. In this case, sufficient polymerization occurs during exposure in the pattern formation step, and a pattern having excellent heat resistance, light resistance, and chemical resistance can be formed.

[0090] For example, the compound containing at least two functional groups represented by Chemical Formula 3 may be a compound represented by either Chemical Formula 4 or Chemical Formula 5 below.

[0091] [ka]

[0092] In Chemical Formula 4 and Chemical Formula 5, p, q, r, and s are each independently an integer of 1 to 10.

[0093] The photopolymerizable compound can also be used after being treated with an acid anhydride in order to impart better developability.

[0094] The photopolymerizable compound may be contained in an amount of 1 to 30 parts by weight, for example, 5 to 15 parts by weight, per 100 parts by weight of the resin. When the photopolymerizable compound is contained within the above range, curing occurs sufficiently, and the resulting pattern has excellent reliability, heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion.

[0095] (C) Photopolymerization initiator The photosensitive resin composition according to an embodiment may include a photopolymerization initiator, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

[0096] 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.

[0097] Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0098] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0099] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0100] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-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-triazine. azine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

[0101] Examples of oxime compounds that can be used include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one. Specific examples of O-acyloxime compounds that can be used include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0102] In addition to the compounds described above, the photopolymerization initiator may also be a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a non-imidazole-based compound, a fluorene-based compound, or the like.

[0103] The photopolymerization initiator may be contained in an amount of 1 to 10 parts by weight, for example, 1 to 7 parts by weight, relative to 100 parts by weight of the resin. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently, improving the sensitivity of the resin and the light transmittance of the cured resin.

[0104] (D) Solvent As the solvent, a substance that is compatible with the resin, the photopolymerizable compound, and the photopolymerization initiator but does not react with them can be used.

[0105] Examples of the solvent include alcohols such as methanol and ethanol, ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl 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, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxypropionic acid methyl ester 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and ethyl 2-ethoxypropionate;2-alkoxypropionic acid alkyl esters such as methyl 2-ethoxypropionate, 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters 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 hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate, pyruvic acid Examples of suitable solvents include ketone acid esters such as ethyl ether, and high-boiling 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.

[0106] The solvent may be contained in an amount of 100 to 500 parts by weight relative to 100 parts by weight of the resin. When the solvent is contained within this range, the photosensitive resin composition can have an appropriate viscosity, thereby improving the processability during the production of the photosensitive resin film.

[0107] (E) Other additives The photosensitive resin composition according to an embodiment may further include an additive as another component.

[0108] The photosensitive resin composition may contain additives such as sensitizers such as diacids (e.g., malonic acid), alkanolamines (e.g., 3-amino-1,2-propanediol, N-phenyldiethanolamine), leveling agents, silane coupling agents, surfactants, epoxy compounds, thermal latent acid generators, development modifiers, curing agents, or combinations thereof, to prevent stains and spots during coating, improve leveling properties, or prevent the generation of residues due to undeveloped coating. The amounts of these additives used can be adjusted appropriately depending on the desired physical properties.

[0109] For example, a silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion to a substrate, and has a structure different from that of a silane compound.

[0110] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these can be used alone or in combination of two or more.

[0111] The silane coupling agent may be contained in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, a photosensitive resin composition having excellent adhesion, storage stability, etc. can be obtained.

[0112] For example, the surfactant is an additive that is added to prevent non-uniformity in film thickness or to improve developability, and can include a fluorine-based surfactant and / or a silicon-based surfactant.

[0113] Examples of fluorine-based surfactants that can be used include those commercially available under the names BM-1000 and BM-1100 manufactured by BM Chemie; Megafac (registered trademark) F142D, Megafac (registered trademark) F172, Megafac (registered trademark) F173, Megafac (registered trademark) F183, and Megafac (registered trademark) F55 manufactured by DIC Corporation; Florad FC-135, Florad FC-170C, Florad FC-430, and Florad FC-431 manufactured by Sumitomo 3M Limited; Surflon (registered trademark) S-112, Surflon (registered trademark) S-11, Surflon (registered trademark) S-131, Surflon (registered trademark) S-141, and Surflon (registered trademark) S-145 manufactured by Asahi Glass Co., Ltd.; and SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 manufactured by Toray Silicone Co., Ltd.

[0114] As the silicone surfactant, commercially available products such as BYK Chem's 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 can be used.

[0115] 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 a photosensitive resin composition having excellent wetting properties for ITO substrates, glass substrates, Si wafers, SiNx wafers, and Cu substrates can be provided.

[0116] The photosensitive resin composition may further contain an epoxy compound as an additive to improve adhesion, etc. Examples of the epoxy compound include epoxy novolac acrylic carboxylate resin, ortho-cresol novolac epoxy resin, phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, and combinations thereof.

[0117] 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 contained within the above range, the storage stability, adhesion strength, and other properties of the photosensitive resin composition can be improved.

[0118] The photosensitive resin composition may further include a thermal latent acid generator. Examples of the thermal latent acid generator include, but are not limited to, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and trifluorobutanesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or combinations thereof.

[0119] The photosensitive resin composition may also contain certain amounts of other additives such as antioxidants and stabilizers within the range that does not impair the physical properties.

[0120] Another embodiment is a photosensitive resin film, such as a semiconductor rewiring layer insulating film, produced by exposing, developing, and curing the above-described photosensitive resin composition.

[0121] The method for manufacturing the photosensitive resin film (semiconductor rewiring layer insulating film) is as follows.

[0122] (1) Coating and film formation stage The 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 been subjected to a predetermined pretreatment to a desired thickness using a method such as spin or slit coating, roll coating, screen printing, or applicator, and then heated at 70°C to 150°C for 1 to 10 minutes to remove the solvent, thereby forming a coating film.

[0123] (2) Exposure stage The resulting photosensitive resin film is irradiated with actinic radiation of 200 to 500 nm through a mask to form the required pattern. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. X-rays and electron beams can also be used in some cases. The exposure dose varies depending on the type and amount of each component of the composition and the thickness of the dried film, but when using a high-pressure mercury lamp, it is 500 mJ / cm. 2 (Based on a 365nm sensor)

[0124] (3) Development stage In the development step, after the exposure step, an alkaline aqueous solution or an organic solvent is used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form a pattern.

[0125] (4) Post-processing stage A post-heating step can be carried out to improve the heat resistance, light resistance, adhesion, crack resistance, chemical resistance, strength, storage stability, etc. of the image pattern obtained by development in the above step. For example, after development, the image can be heated in an oven at 200°C or 400°C under a nitrogen atmosphere for 1 hour or more.

[0126] Another embodiment is a semiconductor element including a photosensitive resin film (semiconductor rewiring layer insulating film). [Example]

[0127] Preferred examples of the present invention will be described below, but the following examples are merely preferred examples of the present invention and the present invention is not limited to these examples.

[0128] (Synthesis of precursor resin) A four-neck flask equipped with a stirrer, temperature controller, nitrogen gas injector, and condenser was charged with 600 g of gamma-butyrolactone (GBL), monoanhydride monomer, and / or dianhydride monomer while passing nitrogen through. 2-Hydroxyethyl methacrylate (HEMA) was then added, and pyridine was added while stirring at room temperature to obtain a reaction mixture. After reacting for 16 hours at room temperature, the reaction mixture was cooled to -10°C, and a solution of dicyclohexylcarbodiimide (DCC) dissolved in 250 g of GBL was added dropwise over 30 minutes. After stirring the reaction mixture for an additional 5 minutes, a solution of 300 g of GBL (diamine monomer) was added over 40 minutes and stirred for an additional 2 hours. After reacting for 1 hour at room temperature, 30 g of ethanol was added and stirred for 1 hour. Next, GBL was added to the reaction solution to bring the solids content to 18%, and the reaction mixture was added to 3 L of ethanol to obtain a precipitate. The resulting polymer was filtered and dissolved in 1.5 L of tetrahydrofuran (THF). The solution was added dropwise to 30 L of water to produce a precipitate, which was then filtered and vacuum dried. The precursor resin was prepared by drying at 50°C under reduced pressure for 24 hours or more. The molecular weight of the resin was confirmed using a polystyrene calibration curve. The types and molar amounts of the dianhydride and diamine monomers used are listed in Table 1 below.

[0129] [Table 1]

[0130] [ka]

[0131] (Production of Photosensitive Resin Composition) Example 1 33 g of the polyamic ester resin of Synthesis Example 1, 48 g of GBL (Gamma butyrolactone) and 12 g of DMSO (Dimethylsulfoxide) as solvents, 4 g of tetraethylene glycol dimethacrylate and 0.6 g of diurethane dimethacrylate as photopolymerizable compounds, 1 g of a silane coupling agent (KBM-573), and 0.1 g of N-phenyldiethanolamine were mixed, and 0.1 g of a fluorine-based leveling agent, F-554 (DIC Corporation), was further 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.

[0132] Example 2 The same procedure as in Example 1 was carried out, except that the polyamic ester resin of Synthesis Example 2 was used instead of the polyamic ester resin of Synthesis Example 1.

[0133] Example 3 The same procedure as in Example 1 was carried out, except that the polyamic ester resin of Synthesis Example 3 was used instead of the polyamic ester resin of Synthesis Example 1.

[0134] Example 4 The same procedure as in Example 1 was carried out, except that the polyamic ester resin of Synthesis Example 4 was used instead of the polyamic ester resin of Synthesis Example 1.

[0135] Example 5 The same procedure as in Example 1 was carried out, except that the polyamic ester resin of Synthesis Example 5 was used instead of the polyamic ester resin of Synthesis Example 1.

[0136] Comparative Example 1 The same procedure as in Example 1 was carried out, except that 4.6 g of tetraethylene glycol dimethacrylate was used as the photopolymerizable compound.

[0137] Comparative Example 2 The same procedure as in Example 2 was carried out, except that 4.6 g of tetraethylene glycol dimethacrylate was used as the photopolymerizable compound.

[0138] Comparative Example 3 The same procedure as in Example 3 was carried out, except that 4.6 g of tetraethylene glycol dimethacrylate was used as the photopolymerizable compound.

[0139] Comparative Example 4 The same procedure as in Example 4 was carried out, except that 4.6 g of tetraethylene glycol dimethacrylate was used as the photopolymerizable compound.

[0140] Comparative Example 5 The same procedure as in Example 5 was carried out, except that 4.6 g of tetraethylene glycol dimethacrylate was used as the photopolymerizable compound.

[0141] Comparative Example 6 The same procedure as in Example 1 was carried out, except that diurethane dimethacrylate was not used.

[0142] (Evaluation 1: Sensitivity evaluation) The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were each coated onto an 8-inch Cu wafer and heated on a hot plate at 100°C for 4 minutes to produce a 7-μm-thick photosensitive resin film. These photosensitive resin films were exposed to light using a Nikon i10c, subjected to double puddling with cyclopentanone for 20 seconds, rinsed with PGMEA for 1 minute, and then cured in a nitrogen atmosphere at 220°C for 2 hours to obtain a cured film with a 20-μm hole pattern. The Exp. Dose (Eop) required to achieve a 20-μm hole pattern was confirmed using a Hitachi CD-SEM for this cured film. The results are shown in Table 2 below.

[0143] (Rating 2: CTE rating) The wafer on which the cured film of Evaluation 1 was formed was immersed in a 1% solution of hydrofluoric acid to obtain a PI film. This film was peeled off and TMA was measured. The temperature was increased at a rate of 10°C / min and scanned up to 400°C. The results are shown in Table 2 below.

[0144] (Evaluation 3: Adhesion strength evaluation) EMC molding was performed on the wafer on which the cured film of Evaluation 1 was formed, and the adhesive strength was measured using a die shear tester (DAGE series 4000PXY manufactured by DAGE Co., Ltd.). The results are shown in Table 2 below.

[0145] (Rating 4: Reliability rating) The wafers on which the hardened film of Evaluation 1 was formed were subjected to 2000 thermal cycles (-55°C to 125°C), which is a reliability test condition. After that, it was confirmed using FE-SEM whether cracks had formed between the PI and Cu. The results are shown in Table 2 below.

[0146] [Table 2]

[0147] In Table 2, OK means that no cracks were observed, and NG means that cracks were observed. Table 2 shows that the photosensitive resin composition according to one embodiment has excellent sensitivity and CTE characteristics, and also has excellent adhesion to copper layers. Furthermore, this photosensitive resin composition also has excellent reliability, and it can be confirmed that it is suitable for use as a composition for semiconductor redistribution layers.

[0148] The present invention is not limited to the above-described embodiments, and can be manufactured in various different forms, and a person skilled in the art to which the present invention pertains should understand that the present invention can be embodied in other specific forms without changing the technical concept or essential features of the present invention. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and are not limiting.

Claims

1. (A) a resin, (B) a photopolymerizable compound containing a compound represented by the following chemical formula 1: (C) a photopolymerization initiator, and (D) a solvent, 【Chemistry 1】 In the above Chemical Formula 1, R １ and R ２ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, L １ ~L ３ are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

2. The R １ and R ２ The photosensitive resin composition according to claim 1 , wherein each of the groups independently represents a methyl group.

3. Said L ２ and L ３ are each independently an unsubstituted C1 to C20 alkylene group.

4. Said L １ is represented by the following chemical formula L, 【Chemistry 2】 In the formula L, R ３ ~R ６ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, provided that R ３ and R ５ At least one of R is a substituted or unsubstituted C1 to C20 alkyl group, ４ and R ６ At least one of the groups is a substituted or unsubstituted C1 to C20 alkyl group, L ４ ~L ６ are each independently an unsubstituted C1 to C20 alkylene group.

5. Said L ５ and L ６ The photosensitive resin composition according to claim 4 , wherein

6. The photosensitive resin composition according to claim 1 , wherein the compound represented by Chemical Formula 1 has an asymmetric structure.

7. The photosensitive resin composition according to claim 1 , wherein the photopolymerizable compound further comprises a compound having a structure different from that of the compound represented by Chemical Formula 1.

8. The resin is a polyamic acid or polyamic ester resin containing a structural unit represented by the following chemical formula 2: 【Transformation 3】 In the above Chemical Formula 2, X １ is a residue derived from a monoanhydride or dianhydride monomer, Y １ is a residue derived from a diamine monomer, R ７ and R ８ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

9. The monoanhydride monomer or dianhydride monomer is represented by the following Chemical Formula 2-1 or Chemical Formula 2-2: 【Chemistry 4】 In the above formula 2-1, L ７ represents a single bond, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-C(=O)O-*, *-NR ０ - * (R ０ is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic linking group, or a combination thereof.

10. 10. The photosensitive resin composition according to claim 9, wherein the resin comprises a residue derived from the monoanhydride monomer represented by Chemical Formula 2-2.

11. The diamine monomer is represented by the following formula 2-3 or 2-4: 【Transformation 5】 In the chemical formula 2-3 and the chemical formula 2-4, R １１ and R １２ are each independently a halogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, 9. The photosensitive resin composition according to claim 8, wherein m1 and m2 each independently represent an integer of 0 to 4.

12. For 100 parts by weight of the resin, The photopolymerizable compound is contained in an amount of 1 part by weight to 30 parts by weight, The photopolymerization initiator is contained in an amount of 1 part by weight to 10 parts by weight, 2. The photosensitive resin composition according to claim 1, wherein the solvent is contained in an amount of 100 to 500 parts by weight.

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

14. A photosensitive resin film produced using the photosensitive resin composition according to any one of claims 1 to 13.

15. The photosensitive resin film according to claim 14, wherein the photosensitive resin film is a semiconductor rewiring layer insulating film.

16. A semiconductor device comprising the photosensitive resin film according to claim 14.

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