Developer for photosensitive resin composition, developing method, and pattern forming method

Abstract

The present invention aims to provide a developer for photosensitive resin compositions, a developing method, and a pattern forming method.

Description

[Technical Field]

[0001] This specification relates to a developer, a developing method, and a pattern forming method for a photosensitive resin composition. More specifically, it relates to a developer, a developing method, and a pattern forming method for a photosensitive resin composition containing a polyimide resin. This application claims the benefit as of the filing date of Korean Patent Application No. 10-2023-0134210, filed with the Korean Intellectual Property Office on October 10, 2023, and all its contents are incorporated herein by reference. [Background technology]

[0002] Interlayer insulating films or surface protective films of semiconductor devices require excellent mechanical properties and high heat resistance, and polyimide-based binder resins with superior properties are used for these purposes.

[0003] With the expanding application of miniaturization technology in the FAB (Fabrication) process, significant changes are also occurring in packaging technology, with a focus on process technologies for manufacturing high-performance, thin, and compact packages.

[0004] In recent years, as fan-out wafer-level packaging (FO-WLP) technology has grown due to changes in semiconductor back-end processing technology, there has been a significant increase in demand for photosensitive polyimides (PID or PSPI) for redistribution (RDL) that are capable of low-temperature curing and possess excellent physical properties.

[0005] Negative-type photosensitive polyimides (PIDs) have relatively superior mechanical properties, but achieving high resolution is difficult. Positive-type photosensitive polyimides can achieve relatively high resolution, but satisfying mechanical property requirements is difficult.

[0006] Furthermore, lithography processes using photosensitive polyimide materials, particularly the developing process, involve the use of hazardous substances such as highly toxic materials, raising safety and environmental pollution concerns.

[0007] Therefore, there is a need for technological development that provides a photosensitive polyimide material with excellent mechanical properties and the ability to achieve high resolution, while also resolving safety and environmental pollution issues. [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a developer, a developing method, and a pattern forming method for a photosensitive resin composition containing a polyimide resin.

[0009] However, the problems that this invention aims to solve are not limited to those mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0010] One embodiment of the present invention provides a developer for a photosensitive resin composition comprising a first organic solvent, wherein the first organic solvent comprises N,N-diethylformamide (DEF), and the photosensitive resin composition comprises a polyimide resin with an imidization rate of 90% or more.

[0011] One embodiment of the present invention provides a method for developing a photosensitive resin composition, comprising the step of developing a photosensitive resin composition that has been exposed to light in a developer.

[0012] One embodiment of this specification provides a pattern-forming method comprising the steps of: providing an insulating film containing a photosensitive resin composition or a cured product thereof; selectively exposing the insulating film to light; and developing the exposed insulating film with a developer. [Effects of the Invention]

[0013] A developer for a photosensitive resin composition according to one embodiment of the present invention can achieve a pattern with improved resolution on an insulating film that has excellent elongation, sensitivity, and / or adhesion to a substrate and is highly reliable.

[0014] Furthermore, a developer for a photosensitive resin composition according to one embodiment of the present invention can realize a pattern with excellent mechanical properties and high resolution on an insulating film containing a polyimide resin, and can improve safety and environmental pollution problems associated with the development process.

[0015] Furthermore, the developing method and pattern forming method according to one embodiment of the present invention can realize a pattern with excellent mechanical properties and high resolution on an insulating film containing a polyimide resin, and can improve safety and environmental pollution problems associated with the developing process.

[0016] The effects of the present invention are not limited to those described above, and other effects not mentioned can be clearly understood by those skilled in the art from this specification and the accompanying drawings. [Brief explanation of the drawing]

[0017] [Figure 1] This image shows a comparison of the resolution evaluation results of the developer solutions for photosensitive resin compositions used in Example 1-1 and Comparative Example 1-1. [Figure 2] This image shows the resolution evaluation results of the developer for the photosensitive resin composition according to Example 1-2. [Figure 3] This image shows the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Examples 1-3. [Figure 4] This image shows the resolution evaluation results of the developer for the photosensitive resin composition according to Comparative Example 1-2. [Figure 5] This image shows the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Comparative Examples 1-3. [Figure 6] This image shows the resolution evaluation results of the developer for the photosensitive resin composition according to Example 2-1. [Figure 7] This image shows the resolution evaluation results of the developer for the photosensitive resin composition according to Example 2-2. [Figure 8] This image shows the resolution evaluation results of the developer for the photosensitive resin composition according to Example 2-3. [Figure 9] This is an image showing the resolution evaluation results of the developer for the photosensitive resin composition according to Example 2-4. [Figure 10] This is an image showing the resolution evaluation results of the developer for the photosensitive resin composition according to Comparative Example 2-1.

Embodiments for Carrying Out the Invention

[0018] Throughout the specification of the present application, when a certain part "includes" a certain component, it means that, unless otherwise stated, it does not exclude other components, and may further include other components.

[0019] Throughout the specification of the present application, when a certain member is "above" another member, it includes not only the case where a certain member is in contact with another member, but also the case where there is another member between the two members.

[0020] Throughout the specification of the present application, the unit "parts by weight" can mean the weight ratio between each component.

[0021] Throughout the specification of the present application, "(meth)acrylate" is used in the general sense of encompassing acrylate and methacrylate.

[0022] Throughout the specification of the present application, the term "monomer unit" means the form in which a monomer has reacted in a polymer, and specifically, it can mean the form in which the monomer has formed the backbone of the polymer, such as the main chain or side chain, through a polymerization reaction.

[0023] Throughout the specification of this application, the "weight-average molecular weight" and "number-average molecular weight" of a compound can be calculated using the molecular weight and molecular weight distribution of that compound. Specifically, a sample sample with a concentration of 1 wt% of the compound is prepared by placing tetrahydrofuran (THF) and the compound in a 1 ml glass bottle. After filtering the standard sample (polystyrene) and the sample sample through a filter (pore size 0.45 μm), the sample is injected into a GPC injector, and the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample sample with the calibration curve of the standard sample. In this case, an Infinity II 1260 (Agilient) can be used as the measuring instrument, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 °C.

[0024] The present invention will be described in more detail below.

[0025] [Developer for photosensitive resin composition] One embodiment of the present invention provides a developer for a photosensitive resin composition comprising a first organic solvent, wherein the first organic solvent comprises N,N-diethylformamide (DEF), and the photosensitive resin composition comprises a polyimide resin with an imidization rate of 90% or more.

[0026] A developer for a photosensitive resin composition according to one embodiment of the present invention can achieve a pattern with improved resolution on an insulating film that has excellent elongation, sensitivity, and / or adhesion to a substrate and is highly reliable.

[0027] Furthermore, a developer for a photosensitive resin composition according to one embodiment of the present invention can realize a pattern with excellent mechanical properties and high resolution on an insulating film containing a polyimide resin, and can improve safety and environmental pollution problems associated with the development process.

[0028] In one embodiment of the present invention, the first organic solvent may contain N,N-diethylformamide (DEF). The N,N-diethylformamide (DEF) may be a component that imparts developability to the developer for the photosensitive resin composition. By including N,N-diethylformamide (DEF) in the first organic solvent, the amount of developing solvents designated as hazardous substances, such as N-methyl-2-pyrrolidone (NMP) and cyclopentanone (CPO), can be reduced, thereby improving safety and environmental pollution issues associated with the development process. Furthermore, by including the polyimide resin described later, it is particularly suitable for development processes and pattern formation methods for insulating films that have excellent elongation, sensitivity, and / or adhesion to the substrate and high reliability, and it is possible to realize patterns with excellent mechanical properties and high resolution on the insulating film.

[0029] In one embodiment of the present invention, the photosensitive resin composition may include a polyimide resin with an imidization rate of 90% or more. Specifically, the photosensitive resin composition may be a photosensitive polyimide resin composition, and the polyimide resin contained in the photosensitive resin composition may have an imidization rate of 90% or more. More specifically, the imidization rate of the polyimide resin may be 90% or more, 92% or more, 94% or more, or 96% or more. This allows the manufactured insulating film to have excellent elongation, sensitivity, and / or adhesion to the substrate, and to have high reliability.

[0030] In one embodiment of the present invention, the developer for the photosensitive resin composition may be a developer for a photosensitive polyimide resin composition, and the photosensitive polyimide resin composition may have the composition described below, and may contain the photosensitive polyimide resin described below.

[0031] In one embodiment of the present invention, the developer for the photosensitive resin composition may contain a first organic solvent.

[0032] In one embodiment of the present invention, the boiling point of the first organic solvent may be 160°C or higher and 200°C or lower. Specifically, the boiling point of the first organic solvent may be 165°C or higher, 170°C or higher, or 175°C or higher, and the boiling point of the first organic solvent may be 200°C or lower, 195°C or lower, 190°C or lower, or 185°C or lower. When the boiling point is within the range described above, it is more suitable for the development process of polyimide resin and the development margin of the developer solution containing it can be further improved.

[0033] In one embodiment of the present invention, the flash point of the first organic solvent may be 50°C or higher and 90°C or lower. Specifically, the flash point of the first organic solvent may be 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, and the flash point of the first organic solvent may be 85°C or lower, 80°C or lower, 75°C or lower, or 70°C or lower. When the flash point is within the range described above, it is more suitable for the development process of polyimide resin, and the safety of the developer containing it can be further improved.

[0034] In one embodiment of the present invention, the content of N,N-diethylformamide may be 20 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the first organic solvent. Specifically, the content of N,N-diethylformamide may be 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more per 100 parts by weight of the first organic solvent, and may be 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, or 80 parts by weight or less. When the content of N,N-diethylformamide satisfies the above range, it is possible to realize a pattern with excellent mechanical properties and high resolution on an insulating film containing polyimide resin, and it is possible to improve safety problems and environmental pollution problems associated with the development process.

[0035] In one embodiment of the present invention, the N,N-diethylformamide may be used as the main solvent of the developer for the photosensitive resin composition. In other words, the content of the N,N-diethylformamide may be 50 parts by weight or more per 100 parts by weight of the first organic solvent. When the N,N-diethylformamide is used as the main solvent of the developer for the photosensitive resin composition, the development margin of the formed pattern can be further improved, and the effect of improving safety issues and environmental pollution issues associated with the development process can be further improved.

[0036] In one embodiment of the present invention, the first organic solvent may further comprise a polar organic solvent. Specifically, the polar organic solvent may be a polar aprotic organic solvent. More specifically, the polar organic solvent may be any one selected from dimethyl sulfoxide, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylacrylamide, cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, γ-butyrolactone, α-acetyl-γ-butyrolactone, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, and mixtures thereof. For example, the first organic solvent may further comprise cyclopentanone (CPO). When the first organic solvent further comprises a polar organic solvent, the develop margin of the formed pattern can be further improved, and the solubility in the photosensitive resin composition can be further improved.

[0037] The polar organic solvent imparts developability to the developer for the photosensitive resin composition and is soluble in the photosensitive resin composition, and may be an organic solvent commonly used in the industry.

[0038] In other words, the first organic solvent may be N,N-diethylformamide (DEF) alone, or a mixture of N,N-diethylformamide (DEF) and a polar organic solvent other than N,N-diethylformamide (DEF).

[0039] [Photosensitive resin composition] One embodiment of the present invention provides a photosensitive resin composition comprising a polyimide resin, the photosensitive resin composition comprising a polyimide resin described later.

[0040] A photosensitive resin composition according to one embodiment of the present invention comprises a polyimide resin and may further contain a photoacid generator.

[0041] In one embodiment of the present invention, the photoacid generator is used to enable the photosensitive resin composition to act as a chemically amplified composition, and by effectively controlling the acid diffusion length, the resolution of the pattern can be improved. Any conventional photoacid generator can be used as the photoacid generator, and preferably, ionic photoacid generators, sulfonyldiazomethane-based, N-sulfonyloxyimide-based, benzoin sulfonate-based, nitrobenzyl sulfonate-based, sulfone-based, glyoxime-based, and triazine-based agents may be used.

[0042] In one embodiment of the present invention, the photosensitive resin composition may further contain additives. Specifically, the additives may further contain one or more of the following: surfactants, antioxidants, and crosslinking agents.

[0043] In one embodiment of the present invention, the photosensitive resin composition may contain any of the additives: a surfactant, an antioxidant, and a crosslinking agent.

[0044] In one embodiment of the present invention, the surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, as a silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, manufactured by BYK-Chemie, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. may be used as fluorine-based surfactants. DIC (DaiNippon Ink & F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F (manufactured by Chemicals) -487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but are not limited to these.

[0045] In one embodiment of the present invention, the antioxidant can play a role in improving the elongation characteristics of the cured film and its adhesion to metal materials. Furthermore, the antioxidant can suppress oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of the polyimide resin and suppress metal oxidation by providing rust prevention to metal materials. Specific examples of the antioxidant include, but are not limited to, the following compounds.

[0046] In one embodiment of the present invention, the crosslinking agent is not particularly limited and can be used without restriction as long as it is applicable to the art. The crosslinking agent may mainly be a thermal crosslinking agent or a radical monomer. Examples of the crosslinking agent include, but are not limited to, compounds having at least two alkoxymethyl groups and / or methylol groups, and compounds having at least two epoxy groups and / or oxetanyl groups. By including the compounds exemplified above, a condensation reaction can occur with the resin of the present invention during firing after patterning to form a crosslinked structure, thereby improving the mechanical properties of the cured resin pattern, such as elongation. Furthermore, two or more types of crosslinking agents may be used in combination. This allows for a variety of designs.

[0047] In one embodiment of the present invention, preferred examples of compounds having at least two alkoxymethyl groups and / or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, and DMOM Examples include -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOMBPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC® MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), which are available from various companies. Two or more of these may be included.

[0048] Furthermore, preferred examples of compounds having at least two epoxy groups and / or oxetanyl groups include, but are not limited to, bisphenol A type epoxy resin, bisphenol A type oxetanyl resin, bisphenol F type epoxy resin, bisphenol F type oxetanyl resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, EPICLON® 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON Examples include EXA-4822 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin® BEO-60E (trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Corporation), and others, all of which are available from various companies. Two or more of these may be included.

[0049] Furthermore, as the crosslinking agent, 2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]propan-2-yl]phenoxy]methyl]oxirane, tetraethylene glycol dimethyl acrylate, and the like may be used.

[0050] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 10 parts by weight or more, per 100 parts by weight of the total polyimide resin, and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by weight or less, and more preferably 200 parts by weight or less.

[0051] In one embodiment of the present invention, in order to improve the resolution of the relief pattern, the photosensitive resin composition may further contain monomers having photopolymerizable unsaturated bonds. Preferred monomers are (meth)acrylic compounds that undergo radical polymerization reactions with a photopolymerization initiator, and are not particularly limited to the following, but include, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, mono or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, and 1,6-hexanediol. Examples of compounds include xanediol diacrylates and dimethacrylates, neopentyl glycol diacrylates and dimethacrylates, bisphenol A mono- or diacrylates and methacrylates, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylate and methacrylate, pentaerythritol di-, tri- or tetraacrylate and methacrylate, and ethylene oxide or propylene oxide adducts of these compounds.

[0052] The content of the monomer having the photopolymerizable unsaturated bond is preferably 1 to 50 parts by weight per 100 parts by weight of the total polyimide resin.

[0053] In one embodiment of the present invention, the photosensitive resin composition comprises a second organic solvent, the second organic solvent may also comprise N,N-diethylformamide (DEF).

[0054] In one embodiment of the present invention, the content of N,N-diethylformamide may be 20 parts by weight or more and 80 parts by weight or less per 100 parts by weight of the second organic solvent. Specifically, the content of N,N-diethylformamide may be 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more per 100 parts by weight of the second organic solvent, and may be 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, or 60 parts by weight or less. When the content of N,N-diethylformamide satisfies the above range, an insulating film with excellent elongation, sensitivity, and / or adhesion to the substrate and high reliability can be realized.

[0055] In one embodiment of the present invention, the second organic solvent may further include compounds known to enable the formation of photosensitive resin compositions in the art to which the present invention belongs. Specifically, the second organic solvent may further include one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0056] The aforementioned ester compounds include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) It may also be methyl 2-oxypropionate, alkyl 2-oxypropionate esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.).

[0057] The ether compounds may include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

[0058] The ketone compounds may include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.

[0059] The aforementioned aromatic hydrocarbon compound may be toluene, xylene, anisole, limonene, or the like.

[0060] The aforementioned sulfoxide compounds may include dimethyl sulfoxide, among others.

[0061] In one embodiment of the present invention, the photosensitive resin composition is 350 mJ / cm³ 2 It may have the following sensitivities.

[0062] In one embodiment of the present invention, the photosensitive resin composition is approximately 350 mJ / cm³ 2 Below, approximately 340mJ / cm 2 Below, approximately 330mJ / cm 2 Below, approximately 320mJ / cm 2 The following, or approximately 310 mJ / cm² 2 The sensitivity may be as follows. The lower limit of sensitivity is not particularly limited, but is approximately 350 mJ / cm². 2 If the following values ​​are obtained, it can be determined that the photosensitive material has excellent physical properties (for example, easy development of fine patterns).

[0063] In one embodiment of the present invention, the photosensitive resin composition may contain 1 to 40 parts by weight of the photoacid generator; 5 to 50 parts by weight of the crosslinking agent; and 0.05 to 5 parts by weight of the surfactant, per 100 parts by weight of the polyimide resin.

[0064] In one embodiment of the present invention, the photosensitive resin composition may contain 50 to 500 parts by weight of the solvent per 100 parts by weight of the polyimide resin.

[0065] When each of the above-mentioned components is included in the photosensitive resin composition in the aforementioned range of parts by weight, sensitivity and physical properties, as well as substrate adhesion, can be improved even with the use of a small amount of photoacid generator.

[0066] In one embodiment of the present invention, the photosensitive resin composition may be a negative-type photosensitive composition. Specifically, the photosensitive resin composition may be at least partially exposed, i.e., the exposed portion may undergo imidization of the precursor contained in the photosensitive resin composition, resulting in a decrease in its solubility in the aforementioned developer for photosensitive resin compositions, while the unexposed portion may be soluble in the aforementioned developer for photosensitive resin compositions. As a result, when the photosensitive resin composition is developed with the aforementioned developer for photosensitive resin compositions, the unexposed portion is dissolved and removed in the developer, while the exposed portion may remain because its solubility in the developer is insufficient. Examples of development methods include, but are not limited to, shower development, spray development, immersion development, and paddle development.

[0067] [Polyimide resin] In one embodiment of the present invention, the polyimide resin may include a structure represented by any one of the following chemical formulas 1 to 3.

[0068] [ka]

[0069] In the above chemical formulas 1 to 3,

[0070] [ka]

[0071] This refers to the part that is bonded to other substituents or repeating units. L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -SO2-; -CO-; or -OCO-. L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-. R1 and R2 are either identical or different from each other, and independently are hydrogen; or a substituted or unsubstituted alkyl group. R3 and R4 are either identical or different from each other, and independently are hydrogen; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and independently integers between 0 and 3. If r1 is 2 or greater, then R1 is either identical or different. If r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or the structure represented by the following chemical formula a.

[0072] [ka]

[0073] In the aforementioned chemical formula a,

[0074] [ka]

[0075] This refers to the portion connected to chemical formula 1 or chemical formula 2, R5 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

[0076] According to one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 1.

[0077] According to one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 2.

[0078] According to one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 3.

[0079] According to one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 1 and the structure represented by chemical formula 2.

[0080] According to one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 1 and the structure represented by chemical formula 3.

[0081] According to one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2 and the structure represented by chemical formula 3.

[0082] According to one embodiment of the present invention, the polyimide resin may include a structure represented by chemical formula 1 or chemical formula 3, and a structure represented by chemical formula 2.

[0083] According to one embodiment of the present invention, the polyimide resin may contain any of the structures represented by chemical formulas 1 to 3.

[0084] A polyimide resin according to one embodiment of the present invention contains a flexible chain and a protection group that is alkali-insoluble to acids, and can be given meltability under high-temperature conditions, thus having the advantages of improved elongation, hydrophilicity, and excellent substrate adhesion. Compared to photosensitive resin compositions that use photoinitiators (PIs) commonly used in the art, the photosensitive resin composition containing the polyimide resin requires less photoacid generator (PAG) when applied, making it easier to realize fine patterns and providing excellent resolution. Furthermore, the photosensitive resin composition according to this specification can provide a large quantity of photosensitive resin compositions with excellent sensitivity even when using a small amount of photoacid generator.

[0085] Specifically, the polyimide resin according to one embodiment of the present invention contains a flexible chain containing an ester or ether group, which gives it hydrophilicity and meltability at high temperatures (approximately 100°C to 200°C), thus improving substrate adhesion. Furthermore, the flexible chain imparts flexibility to the polyimide resin, improving elongation and suppressing wafer warping. In addition, it lowers the glass transition temperature (Tg) of the polyimide resin, which helps in the diffusion of the photoacid generator contained in the negative-type photosensitive resin composition, thereby improving resolution.

[0086] In this specification,

[0087] [ka]

[0088] This refers to a site that bonds to another substituent or bond, and may refer to a site that bonds to the main chain of the polymer as specified herein.

[0089] In this specification, "polymer" means a compound consisting of repeating units (basic units). The polymer may also be represented by a polymer or a compound consisting of a polymer.

[0090] Examples of substituents described herein are, but are not limited to, those listed below.

[0091] In this specification, the terms “substituted or unsubstituted” mean substituted with one or more substituents selected from the group consisting of deuterium; halogen groups; nitrile groups; nitro groups; hydroxyl groups; -COOH; alkoxy groups; alkyl groups; cycloalkyl groups; alkenyl groups; cycloalkenyl groups; aryl groups; heteroaryl groups; and heterocyclic groups containing one or more O, N, or S atoms, or having no substituents at all.

[0092] In this specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

[0093] In this specification, the alkoxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 30, more specifically 1 to 20, and more specifically 1 to 10.

[0094] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. In one embodiment, the alkyl group has 1 to 30 carbon atoms. In another embodiment, the alkyl group has 1 to 20 carbon atoms. In yet another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. In this specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and is particularly preferably a cyclopentyl group or a cyclohexyl group, but is not limited to these.

[0095] In this specification, the alkylene group is subject to the description of alkyl groups described above, except that the alkyl group is divalent.

[0096] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. In one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0097] In this specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. In one embodiment, the number of carbon atoms of the alkyl group is 2 to 30. In another embodiment, the number of carbon atoms of the alkyl group is 2 to 20. In yet another embodiment, the number of carbon atoms of the alkyl group is 2 to 10. Specific examples of the alkenyl group include, but are not limited to, alkenyl groups substituted with aryl groups such as stylbenyl and styrenyl.

[0098] In this specification, the cycloalkenyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. In one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Examples of the cycloalkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl groups.

[0099] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. In one embodiment, the aryl group has 6 to 30 carbon atoms. In one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, and terphenyl groups. Examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, indenyl, phenantrenyl, pyrenyl, perilenyl, triphenyl, chrysenyl, and fluorenyl groups.

[0100] In this specification, the arylene group is described in the same way as the aryl group described above, except that the arylene group is divalent.

[0101] In this specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms. Examples of the heterocyclic group include, but are not limited to, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, an acridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuran group, a dibenzofuran group, a tetrahydropyran, and the like. Preferably, the heterocyclic group is a tetrahydropyran.

[0102] In this specification, the description of heterocyclic groups described above may apply to the heteroaryl group, except that it is aromatic.

[0103] In this specification, the aromatic ring may be an aryl group or a heteroaryl group, and the aryl group or heteroaryl group may be subject to the above description. The aliphatic ring may mean a ring other than the aromatic ring.

[0104] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0105] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0106] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0107] In one embodiment of the present invention, L11 may be directly bonded; a halogen-substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -SO2-; -CO-; or -OCO-.

[0108] In one embodiment of the present invention, L12 may be directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-.

[0109] In one embodiment of the present invention, L12 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0110] In one embodiment of the present invention, L12 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0111] In one embodiment of the present invention, L12 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0112] In one embodiment of the present invention, L12 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or -O-.

[0113] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0114] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C20 alkyl group.

[0115] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0116] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0117] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C20 alkyl group.

[0118] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0119] In one embodiment of the present invention, Ra and Rb may be the same or different from each other, and each may independently be hydrogen; or a structure represented by the following chemical formula a.

[0120] [ka]

[0121] In one embodiment of the present invention, the chemical formula a may be any one of the following structures, and the value of q must satisfy an integer from 1 to 10, and is not limited to the following examples.

[0122] [ka]

[0123] In one embodiment of the present invention, R5 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0124] In one embodiment of the present invention, R5 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0125] In one embodiment of the present invention, R5 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0126] In one embodiment of the present invention, at least one of Ra and Rb contains a structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be greater than 0 mol% and less than or equal to 100 mol% of the total content of the polyimide resin.

[0127] In one embodiment of the present invention, at least one of Ra and Rb contains the structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be 10 mol% to 100 mol%, 20 mol% to 100 mol%, 30 mol% to 100 mol%, 40 mol% to 100 mol%, 50 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 80 mol% to 100 mol%, 90 mol% to 100 mol%, or 100 mol% relative to the total content of the polyimide resin.

[0128] In one embodiment of the present invention, the content of the structure represented by chemical formula a relative to the total content of the polyimide resin can be confirmed by commercially available NMR. After the resin synthesis reaction is complete, the amount of OH before the reaction can be derived from the number of protons of the entire aromatic ring of the polyimide, and the content (mol%) of the structure represented by chemical formula a can be confirmed by the number of protons of chemical formula a (integration of the 6.41-5.83 ppm (3H) peak) relative to the amount of OH before the reaction.

[0129] In one embodiment of the present invention, chemical formulas 1 to 3 may be represented by any one of the following structural formulas.

[0130] [ka]

[0131] In the above structural formula, Ra and Rb are defined as in the above chemical formulas 1 and 2.

[0132] [ka]

[0133] This can refer to a portion that bonds to other substituents or repeating units.

[0134] In one embodiment of the present invention, the polyimide resin may further include a structure represented by the following chemical formula E-1 or chemical formula E-2.

[0135] [ka]

[0136] In the aforementioned chemical formulas E-1 and E-2,

[0137] [ka]

[0138] This refers to the part that is bonded to other substituents or repeating units. Re1 is hydrogen; or a substituted or unsubstituted alkyl group. re1 is an integer between 0 and 4, and if re1 is 2 or greater, then any Re1 values ​​greater than or equal to 2 are either identical or different from each other. Re is hydrogen; or the structure represented by the chemical formula a above.

[0139] In one embodiment of the present invention, the structure represented by chemical formula E-1 or chemical formula E-2 may be an end group of the polyimide resin.

[0140] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0141] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0142] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0143] In one embodiment of the present invention, Re may be hydrogen; or the structure represented by the chemical formula a.

[0144] In one embodiment of the present invention, Re has the structure represented by the chemical formula a. The details of the chemical formula a are as described above.

[0145] In one embodiment of the present invention, the polyimide resin may further include a structure represented by the following chemical formula E-2 as an end group.

[0146] [ka]

[0147] In the aforementioned chemical formula E-2,

[0148] [ka]

[0149] This refers to the part that is bonded to other substituents or repeating units. Re1 is hydrogen; or a substituted or unsubstituted alkyl group. re1 is an integer between 0 and 4, and if re1 is 2 or greater, then any Re1 values ​​greater than or equal to 2 are either identical or different from each other. Re is hydrogen; or the structure represented by the chemical formula a above.

[0150] In one embodiment of the present invention, the polyimide resin may further include a structure represented by any one of the following chemical formulas 4-1 to 4-4.

[0151] [ka]

[0152] In the aforementioned chemical formulas 4-1 to 4-4,

[0153] [ka]

[0154] This refers to the part that is bonded to other substituents or repeating units. L21~L23 are either identical or different to each other, and each is independently directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-. L' and L'' are identical or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being either identical or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is either identical or different from the others. If ra2 is 2 or greater, then Ra2 is either identical or different from the others. If ra3 is 2 or greater, then Ra3 is either identical or different from the others. If ra4 is 2 or greater, then Ra4 is either identical or different from the others. If ra5 is 2 or greater, then Ra5 is either identical or different from the others. If ra6 is 2 or greater, then Ra6 is either identical or different from the others. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

[0155] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0156] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0157] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0158] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0159] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0160] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0161] In one embodiment of the present invention, the structure represented by any one of the chemical formulas 4-1 to 4-4 may be derived from any one of the following chemical formulas.

[0162] [ka] [ka]

[0163] In one embodiment of the present invention, the weight-average molecular weight of the polyimide resin may be 3,000 g / mol to 70,000 g / mol. Specifically, the weight-average molecular weight of the polyimide resin may be 5,000 g / mol to 50,000 g / mol. If the weight-average molecular weight of the polyimide resin is less than 3,000 g / mol, the resulting insulating film may be easily damaged or the adhesive strength may decrease. Furthermore, if the weight-average molecular weight of the polyimide resin exceeds 70,000 g / mol, the sensitivity may decrease and development may fail, or residues (e.g., scum) may remain, which is undesirable.

[0164] [Method for developing and pattern forming a photosensitive resin composition] One embodiment of the present invention provides a method for developing a photosensitive resin composition, comprising the step of developing a photosensitive resin composition that has been exposed to light in the aforementioned developer for photosensitive resin compositions.

[0165] Furthermore, one embodiment of the present invention includes the steps of: providing an insulating film containing a photosensitive resin composition or a cured product thereof; selectively exposing the insulating film to light; and The present invention provides a pattern forming method that includes the step of developing the exposed insulating film with the aforementioned developing solution.

[0166] The following explains each stage.

[0167] According to one embodiment of the present invention, the step of providing the insulating film may involve applying and curing the photosensitive resin composition on the surface of the object to be coated.

[0168] The coating method is not particularly limited, but spray coating, roll coating, spin coating, etc., may be used, and generally, spin coating is the most commonly used method. In addition, after forming the coated film, the residual solvent may be partially removed under reduced pressure if necessary.

[0169] Examples of light sources for curing a photosensitive resin composition according to one embodiment of the present invention include, but are not limited to, a mercury vapor arc (arc), a carbon arc, or a xenon (Xe) arc that emit light with a wavelength of 250 nm to 450 nm.

[0170] The insulating film may be further subjected to a heat treatment step, if necessary, after the photosensitive resin composition has been cured.

[0171] The aforementioned heat treatment may be carried out using heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 180°C to 250°C, or 190°C to 220°C.

[0172] According to one embodiment of the present invention, the step of selectively exposing the insulating film may be to selectively expose the provided insulating film to a predetermined pattern. The selective exposure may usually be performed using a mask including a predetermined pattern.

[0173] The exposure may be performed using ultraviolet rays, electron beams, laser beams, etc. emitted from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, an i-line stepper, etc. The exposure amount may be adjusted according to the light source used, the film thickness of the coating film, etc., but generally it is 1 to 1000 mJ / cm 2 , preferably 10 to 500 mJ / cm 2 may be.

[0174] According to one embodiment of the present invention, the step of developing the exposed insulating film with the above-described developer may be to develop the insulating film selectively exposed to a predetermined pattern with the above-described developer. Thereby, the unexposed portion can be dissolved by the developer for the photosensitive resin composition described above and removed from the selectively exposed insulating film.

[0175] [Insulating film] One embodiment of the present specification provides an insulating film including the above-described photosensitive resin composition or a cured product thereof.

[0176] The insulating film may contain the photosensitive resin composition as it is.

[0177] The insulating film may contain a cured product of the photosensitive resin composition.

[0178] The insulating film exhibits excellent chemical resistance and mechanical properties, and is preferably applicable to an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, etc. Further, the insulation is applicable to a photoresist, an etching resist, a solder top resist, etc.

[0179] The insulating film may include a support or a substrate.

[0180] The support or substrate is not particularly limited and may be one known in the art. Examples include electronic component substrates and substrates on which a predetermined wiring pattern is formed. Examples of substrates include metal substrates such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, and nickel, as well as glass substrates. Examples of materials for the wiring pattern include copper, solder, chromium, aluminum, nickel, and gold, but are not limited to these. Preferably, the support or substrate may be a silicon wafer.

[0181] In one embodiment of the present invention, the thickness of the insulating film may be 1 μm to 100 μm. When the thickness of the insulating film is within the specified range, an insulating film with excellent chemical resistance and mechanical properties as intended by this specification can be obtained. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0182] [Semiconductor device] One embodiment of the present invention provides a semiconductor device including the insulating film.

[0183] The semiconductor device may be manufactured to include, in addition to the insulating film, various components commonly used in the art.

[0184] The present invention will be described in detail below with reference to examples. However, the examples of the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples herein are provided to give a more complete explanation of the present invention to a person of average skill in the art. [Examples]

[0185] Polymerization example Polymerization Example 1 0.8 eq of 6FODA (2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether) and 0.2 eq of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (Bis-APAF) were dissolved in DEF (Diethyl formamide) under an N2 atmosphere. The mixture was then stirred while heating to 80°C until completely dissolved. 4,4'-Oxydiphthalic anhydride (ODPA) and 5-norbornene-2,3-dicarboxylic anhydride (NDA) were added, a Dean-Stark was coupled, and the mixture was reacted for 6 hours. The mixture was then heated to 150°C and reacted overnight. Residual monomers and cyclization rate were confirmed by NMR, and the reaction was terminated to obtain a polymerization solution. Subsequently, the obtained polymerization solution was diluted with tetrahydrofuran (THF), precipitated with methanol (MeOH), and dried to produce the solid content of polymer 1. The weight-average molecular weight was confirmed to be 35,000 g / mol when measured using gel permeation chromatography (GPC), and the glass transition temperature (Tg) was confirmed to be 245°C when measured using differential scanning calorimetry (DSC).

[0186] [ka]

[0187] In the aforementioned polymer 1, q is a value where the weight-average molecular weight of the polymer is 35,000 g / mol. q is an integer between 5 and 40.

[0188] Synthesis Example 1 To polymer 1 produced in polymerization example 1, 0.016 eq of triethylamine and 0.1 eq of 2-acryloyloxyethyl isocyanate were added relative to the OH group of the polyimide. After setting up an oil bath, the reaction was carried out overnight at 60°C. The reaction was terminated when the 2H peak at 4.25 ppm of AOI (2-acryloyloxyethyl isocyanate) disappeared by NMR.

[0189] The total OH of polymer 1 was calculated by comparing the total area of ​​aromatic rings of the polymer appearing at concentrations above 7 ppm on NMR with the input amount, and the substitution rate of AOI was confirmed by the area of ​​the peak (peak, 3H) appearing at around 6 ppm relative to the total OH. It was confirmed that the polymer was substituted with 10 mol% AOI. The weight-average molecular weight was confirmed to be 19,000 g / mol when measured using gel permeation chromatography (GPC), and the glass transition temperature (Tg) was confirmed to be 260°C when measured by differential scanning calorimetry (DSC).

[0190] The structure of the polymer produced by the above synthesis example 1 is as follows.

[0191] [ka]

[0192] In the polymerization of the above synthesis example 1, q is a value where the weight-average molecular weight of the polymer is 36,000 g / mol. q is an integer between 5 and 40.

[0193] Manufacturing example Manufacturing Example 1 - Production of a photosensitive resin composition A photosensitive resin was prepared using the method described in Synthesis Example 1. Subsequently, 8.4 parts by weight of RP-1040 (Nippon Kayaku Co., Ltd.) and 0.4 parts by weight of TCL-005 (LGC Co., Ltd.) as crosslinking agents, 1.85 parts by weight of OXE-04 (BASF Corporation) as a photoradical initiator, 0.18 parts by weight of KBM503 (Shin-etsu Co., Ltd.) as a coupling agent as an additive, and 0.02 parts by weight of BYK-307 (BYK-Chemie Co., Ltd.) as a surfactant were added to 100 parts by weight of the photosensitive resin in 60 parts by weight of a second organic solvent, which was a mixture of N,N-diethylformamide (DEF) and γ-butyrolactone (GBL) in a weight ratio of 55:5, to produce a photosensitive resin composition. At this time, the solid content of the photosensitive resin composition was 39.00% by weight.

[0194] Manufacturing Example 2-1 - Manufacturing of Polyimide Film The photosensitive resin composition of Production Example 1 was cured under the following conditions to produce the polyimide film of Production Example 2-1. Specifically, the produced photosensitive resin composition was spin-coated to a thickness of 10 μm onto a Si wafer substrate, and then soft-baked on a hot plate set to 90°C to 130°C. After that, it was exposed using an i-line stepper (365 nm) light source with an exposure dose of 400 to 900 mJ, and then post-baked in a nitrogen atmosphere and an oven set to 160°C to 230°C for 20 to 240 minutes to produce the polyimide film.

[0195] Manufacturing Example 2-2 - Manufacturing of Polyimide Film The polyimide film of Production Example 2-2 was manufactured in the same manner as the polyimide film of Production Example 2-1, except that the photosensitive resin composition of Production Example 1 was spin-coated to a thickness of 11.5 μm onto a Si wafer substrate.

[0196] Resolution evaluation Example 1-1 A polyimide film was prepared using the method described in Production Example 2-1. It was then exposed using an 8.0 μm (1:1.5 pitch) pattern mask, and developed for 30 seconds (Spray PGMEA 20-180 sec rinse) twice with a developer containing 100 wt% N,N-diethylformamide (DEF) as the primary organic solvent.

[0197] Subsequently, the Top Critical Dimension (Top CD) of the pattern surface was measured using an optical microscope (OM), and the Hole Critical Dimension (Hole CD) of the hole bottom was measured using a scanning electron microscope (SEM). The resolution was evaluated by comparing the size of the pattern mask with the size of the formed holes, and the evaluation results are shown in Figure 1 and Table 1.

[0198] Examples 1-2 The resolution was evaluated in the same manner as in Example 1-1, except that exposure was performed using a 10.0 μm (1:1.5 pitch) pattern mask, and the evaluation results are shown in Figure 2 and Table 1.

[0199] Examples 1-3 The resolution was evaluated in the same manner as in Example 1-1, except that exposure was performed using a 15.0 μm (1:1.5 pitch) pattern mask, and the evaluation results are shown in Figure 3 and Table 1.

[0200] Comparative Example 1-1 The resolution was evaluated in the same manner as in Example 1-1, except that 100 wt% cyclopentanone (CPO) was used as the developer, and the evaluation results are shown in Figure 1 and Table 1.

[0201] Comparative Example 1-2 The resolution was evaluated in the same manner as in Examples 1-2, except that 100 wt% cyclopentanone (CPO) was used as the developer, and the evaluation results are shown in Figure 4 and Table 1.

[0202] Comparative Examples 1-3 The resolution was evaluated in the same manner as in Examples 1-3, except that 100 wt% cyclopentanone (CPO) was used as the developer, and the evaluation results are shown in Figure 5 and Table 1.

[0203] [Table 1]

[0204] Figure 1 is an image comparing the resolution evaluation results of the photosensitive resin composition developer according to Example 1-1 and Comparative Example 1-1. Figures 2 and 3 are images showing the resolution evaluation results of the photosensitive resin composition developer according to Example 1-2 and Example 1-3. Figures 4 and 5 are images showing the resolution evaluation results of the photosensitive resin composition developer according to Comparative Example 1-2 and Comparative Example 1-3. Specifically, Figure 1(a) is a scanning electron microscope (SEM) side view image showing the resolution evaluation results of the photosensitive resin composition developer according to Example 1-1, and Figure 1(b) is a scanning electron microscope (SEM) side view image showing the resolution evaluation results of the photosensitive resin composition developer according to Comparative Example 1-1. On the other hand, Figures 2 to 5(a) are optical microscope (OM) images showing the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Example 1-2, Example 1-3, Comparative Example 1-2, and Comparative Example 1-3; Figures 2 to 5(b) are scanning electron microscope (SEM) side images showing the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Example 1-2, Example 1-3, Comparative Example 1-2, and Comparative Example 1-3; and Figures 2 to 5(c) are scanning electron microscope (SEM) top images showing the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Example 1-2, Example 1-3, Comparative Example 1-2, and Comparative Example 1-3.

[0205] Referring to Table 1 and Figure 1, the resolution evaluation results for Example 1-1 and Comparative Example 1-1 show that the Top CD relative to the Hole CD, i.e., the value of the pattern surface diameter relative to the hole bottom diameter, is similar to 1.2, confirming that they have an equivalent or improved level of resolution.

[0206] On the other hand, the size of the formed pattern can be measured from OM images or SEM images. However, in the case of OM, the accuracy is low due to the resolution and limiting magnification. Therefore, the shape of the formed holes, unevenness in the cured film, and presence or absence of residue were checked from the OM images, and the size of the holes was measured more accurately using SEM images. Referring to Table 1 and Figures 2 to 5(a), the resolution evaluation results for Examples 1-2 or 1-3 using DEF as the developer showed that the shape of the formed holes was better and there was no unevenness or residue compared to the resolution evaluation results for Comparative Examples 1-2 or 1-3 using CPO developer, thus confirming that they have a similar level of high reliability.

[0207] On the other hand, referring to Table 1 and Figures 2 to 5 (b) and (c), the resolution evaluation results for Example 1-2 or Example 1-3 using DEF as the developer were similar to those for Comparative Example 1-2 or Comparative Example 1-3 using CPO developer, with the Top CD relative to Hole CD, i.e., the diameter of the pattern surface relative to the diameter of the hole bottom being 1.1 to 1.2, respectively, confirming that the shape of the formed holes was good.

[0208] This demonstrates that a developer for a photosensitive resin composition according to one embodiment of the present invention has a high flash point, low volatility, excellent safety, and can produce patterns with high resolution.

[0209] Example 2-1 The polyimide film produced in Production Example 2-2 was prepared, and the resolution was evaluated in the same manner as in Example 1-1, except that development for 50 seconds (Spray PGMEA 20-180 sec rinse) was repeated twice with a developer containing 100 wt% N,N-diethylformamide (DEF) as the first organic solvent. The evaluation results are shown in Figure 6 and Table 2.

[0210] On the other hand, the minimum achievable resolution was further evaluated as a resolution evaluation element, and the evaluation results are shown in Table 2 below. Specifically, exposure and development were performed in the same manner as in Example 1-1, except that a different pattern mask was used, and the minimum achievable resolution that allows for the formation of a uniform hole pattern, i.e., the minimum value of Hole Critical Dimension (Hole CD), was measured.

[0211] Example 2-2 The resolution was evaluated in the same manner as in Example 2-1, except that a mixture of 50 wt% N,N-diethylformamide (DEF) and 50 wt% cyclopentanone (CPO) was used as the developer. The evaluation results are shown in Figure 7 and Table 2.

[0212] Examples 2-3 The resolution was evaluated in the same manner as in Example 2-1, except that a mixture of 20 wt% N,N-diethylformamide (DEF) and 80 wt% cyclopentanone (CPO) was used as the developer. The evaluation results are shown in Figure 8 and Table 2.

[0213] Examples 2-4 The resolution was evaluated in the same manner as in Example 2-1, except that a mixture of 10 wt% N,N-diethylformamide (DEF) and 90 wt% cyclopentanone (CPO) was used as the developer, and the evaluation results are shown in Figure 9 and Table 2.

[0214] Comparative Example 2-1 The resolution was evaluated in the same manner as in Example 2-1, except that 100 wt% cyclopentanone (CPO) was used as the developer, and the evaluation results are shown in Figure 10 and Table 2.

[0215] [Table 2]

[0216] Figures 6 to 9 show the resolution evaluation results of the developer solutions for photosensitive resin compositions according to Examples 2-1 to 2-4, and Figure 10 shows the resolution evaluation results of the developer solution for photosensitive resin compositions according to Comparative Example 2-1. Referring to Table 2 and Figures 6 to 10, it was confirmed that the resolution evaluation results for Examples 2-1 to 2-4 and Comparative Example 2-1 showed that the value of Top CD relative to Hole CD, i.e., the value of the diameter of the pattern surface relative to the diameter of the hole bottom, was 1.2 or less, indicating an equivalent or improved level of resolution. Specifically, it was confirmed that as the DEF ratio of the developer increased, Top CD remained similar, but Hole CD increased. This confirmed that the value of Top CD relative to Hole CD, i.e., the value of the diameter of the pattern surface relative to the diameter of the hole bottom, decreased, and the resolution improved.

[0217] In particular, referring to Figures 6 to 8, in Examples 2-1 to 2-3, where the DEF content of the developer was 20 wt% or more, the shape of the formed holes was good, and it was confirmed that the value of Top CD relative to Hole CD, i.e., the diameter of the pattern surface relative to the diameter of the hole bottom, was further improved to 1.0 or 1.1. Specifically, it was confirmed that as the proportion of DEF increased, the Hole CD increased, and the realization of fine patterns tended to become easier. Furthermore, in Examples 2-1 to 2-3, the minimum achievable resolution was 8 μm, confirming that the realization of fine patterns was easier.

[0218] Furthermore, referring to Figures 6 and 7, it was confirmed that in Examples 2-1 and 2-2, where DEF was 50 wt% or more and was the main solvent of the developer, the resolution evaluation results were better compared to cases where DEF was not the main solvent, and that there was a superior improvement in safety and environmental pollution issues.

[0219] This demonstrates that a developer for a photosensitive resin composition according to one embodiment of the present invention has a high flash point, low volatility, excellent safety, and can produce patterns with high resolution.

[0220] In other words, the developer for the photosensitive resin composition according to one embodiment of the present invention can realize a pattern with improved resolution on an insulating film that has excellent elongation, sensitivity, and / or adhesion to the substrate and is highly reliable.

[0221] Furthermore, it can be seen that a developer for a photosensitive resin composition according to one embodiment of the present invention can realize a pattern with excellent mechanical properties and high resolution on an insulating film containing a polyimide resin, and can improve safety and environmental pollution problems associated with the development process.

[0222] The above detailed description is illustrative and illustrative of the present invention. Furthermore, the foregoing is merely an illustration of preferred embodiments of the present invention, and as stated above, the present invention can be used in a variety of other combinations, modifications, and environments, and can be modified or altered within the scope of the concept of the invention disclosed herein, the scope equivalent to the foregoing disclosure, and / or within the scope of the art or knowledge of the art. Accordingly, the above detailed description of the invention is not intended to limit the present invention to the disclosed embodiments. Furthermore, the appended claims should be construed to include other embodiments as well. [Explanation of symbols]

[0223] Top CD ··· Pattern surface diameter Hole CD ···Diameter of the bottom of the hole

Claims

1. A developer for a photosensitive resin composition containing a first organic solvent, The first organic solvent comprises N,N-diethylformamide (DEF), The photosensitive resin composition is a developer for a photosensitive resin composition, comprising a polyimide resin with an imidization rate of 90% or more.

2. The developer for the photosensitive resin composition according to claim 1, wherein the content of N,N-diethylformamide is 20 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the first organic solvent.

3. The developer for a photosensitive resin composition according to claim 1, wherein the first organic solvent further comprises one selected from dimethyl sulfoxide, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylacrylamide, cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, γ-butyrolactone, α-acetyl-γ-butyrolactone, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, and mixtures thereof.

4. The aforementioned polyimide resin is A developer for a photosensitive resin composition according to claim 1, comprising a polyimide resin containing a structure represented by any one of the following chemical formulas 1 to 3: 【Chemistry 1】 In the aforementioned chemical formulas 1 to 3, 【Chemistry 2】 This refers to the part that is bonded to other substituents or repeating units. L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; or -SO ２ -; -CO-; or -OCO-, L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO ２ -; -CO-; or -OCO-, R1 and R2 are either identical or different from each other, and independently are hydrogen; or a substituted or unsubstituted alkyl group. R3 and R4 are either identical or different from each other, and independently are hydrogen; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and each is an integer between 0 and 3, and if r1 is 2 or greater, then R1 is either identical or different, and if r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or a structure represented by the following chemical formula a. 【Transformation 3】 In the aforementioned chemical formula a, 【Chemistry 4】 This refers to the portion connected to chemical formula 1 or chemical formula 2, R5 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

5. The developer for the photosensitive resin composition according to claim 4, wherein the polyimide resin further comprises a structure represented by the following chemical formula E-2 as an end group: 【Transformation 5】 In the aforementioned chemical formula E-2, 【Transformation 6】 This refers to the part that is bonded to other substituents or repeating units. Re1 is hydrogen; or a substituted or unsubstituted alkyl group. re1 is an integer from 0 to 4, and if re1 is 2 or greater, then 2 or greater Re1 values ​​are either identical or different from each other. Re is hydrogen; or the structure represented by the chemical formula a above.

6. The aforementioned polyimide resin is A developer for a photosensitive resin composition according to claim 4, further comprising a structure represented by any one of the following chemical formulas 4-1 to 4-4: 【Transformation 7】 In the aforementioned chemical formulas 4-1 to 4-4, 【Transformation 8】 This refers to the part that is bonded to other substituents or repeating units. L21 to L23 are either identical or different from each other, and each is independently directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')m-O-. L' and L'' are identical or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being the same or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is the same or different from the others; if ra2 is 2 or greater, then Ra2 is the same or different from the others; if ra3 is 2 or greater, then Ra3 is the same or different from the others; if ra4 is 2 or greater, then Ra4 is the same or different from the others; if ra5 is 2 or greater, then Ra5 is the same or different from the others; if ra6 is 2 or greater, then Ra6 is the same or different from the others. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

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

8. The aforementioned photosensitive resin composition comprises a second organic solvent, The developer for the photosensitive resin composition according to claim 1, wherein the second organic solvent comprises N,N-diethylformamide (DEF).

9. The developer for the photosensitive resin composition according to claim 8, wherein the content of N,N-diethylformamide is 20 parts by weight or more and 80 parts by weight or less per 100 parts by weight of the second organic solvent.

10. A method for developing a photosensitive resin composition, comprising the step of developing a photosensitive resin composition that has been exposed to light in at least a portion of it with the developer for photosensitive resin compositions described in claim 1.

11. A step of providing an insulating film containing a photosensitive resin composition or its cured product; A step of selectively exposing the insulating film; and The step of developing the exposed insulating film with the developer for the photosensitive resin composition described in claim 1. A pattern formation method, including the following.

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