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

Abstract

The present disclosure relates to providing a developer solution for a photosensitive resin composition, a developing method, and a pattern forming method.

Description

Technical Field

[0001] This disclosure relates to a developer solution, a development method, and a pattern forming method for a photosensitive resin composition. Specifically, it relates to a developer solution, a development method, and a pattern forming method for a photosensitive resin composition comprising a polyimide resin. This application claims the benefit of Korean Patent Application No. 10-2023-0134210, filed on October 10, 2023, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Background Technology

[0002] Because the interlayer insulating film or surface protective film of semiconductor devices requires excellent mechanical properties and high heat resistance, polyimide binders with excellent physical properties are used.

[0003] With the expansion of FAB (fabrication, assembly, and packaging) processes that employ miniaturization technology, packaging technology is also undergoing significant changes in the process technology for manufacturing high-performance, thin, and small packages.

[0004] With the evolution of semiconductor post-processing technologies, the fan-out wafer-level package (FO-WLP) market has recently experienced continuous growth, and the demand for photosensitive polyimide (PID or PSPI) for redistribution layers (RDLs) is increasing significantly. This photosensitive polyimide can be cured at low temperatures and has excellent physical properties.

[0005] Negative photosensitive polyimide (PID) has relatively good mechanical properties, but it is difficult to achieve high resolution. In the case of positive photosensitive polyimide, although relatively high resolution can be achieved, it is difficult to obtain satisfactory mechanical properties.

[0006] Furthermore, the photolithography process using photosensitive polyimide materials, especially the development process, involves the use of hazardous substances, such as highly toxic substances, which raises concerns about safety and environmental pollution.

[0007] Therefore, there is a need to develop technologies that can address safety and environmental pollution issues while providing photosensitive polyimide materials with excellent mechanical properties and high resolution. Summary of the Invention

[0008] Technical issues

[0009] This disclosure aims to provide a developer solution, a development method, and a patterning method for a photosensitive resin composition comprising a polyimide resin.

[0010] However, the problems to be addressed by this disclosure are not limited to those described above, and those skilled in the art will clearly understand from the following description other problems not mentioned above.

[0011] Technical solution

[0012] An exemplary embodiment of this disclosure provides a developer solution 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 greater.

[0013] An exemplary embodiment of this disclosure provides a development method comprising the step of developing a photosensitive resin composition at least partially exposed to light using the aforementioned developer solution.

[0014] An exemplary embodiment of this disclosure provides a pattern forming method comprising the steps of: providing an insulating film comprising a photosensitive resin composition or a cured product thereof; selectively exposing the insulating film to light; and developing the exposed insulating film with the aforementioned developing agent solution.

[0015] Beneficial effects

[0016] A developer solution for a photosensitive resin composition according to an exemplary embodiment of this disclosure can achieve excellent elongation, sensitivity, and / or adhesion to the substrate and display patterns with improved resolution on the insulating film with high reliability.

[0017] Furthermore, the developer solution used in the photosensitive resin composition can improve safety and environmental pollution issues that arise during the development process, while achieving patterns with excellent mechanical properties and high resolution on the insulating film containing polyimide resin.

[0018] Furthermore, the development method and pattern forming method according to an exemplary embodiment of the present disclosure can improve the safety and environmental pollution problems that occur during the development process, while achieving patterns with excellent mechanical properties and high resolution on an insulating film containing polyimide resin.

[0019] The beneficial effects of this disclosure are not limited to those described above, and those skilled in the art will clearly understand from this specification and the accompanying drawings any effects not mentioned. Attached Figure Description

[0020] Figure 1 Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Examples 1-1 and Comparative Examples 1-1 are shown.

[0021] Figure 2 and Figure 3 Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Examples 1-2 and 1-3 are shown.

[0022] Figure 4 and Figure 5 Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Comparative Examples 1-2 and 1-3 are shown.

[0023] Figures 6 to 9 Images illustrating the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to each of Examples 2-1 to 2-4 are shown.

[0024] Figure 10 This is an image illustrating the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to Comparative Example 2-1. Detailed Implementation

[0025] Throughout this specification, unless the context clearly states otherwise, when a component is described as "including" a component, this does not exclude the presence of another component, but rather means that it may include additional components.

[0026] Throughout this specification, when a component is described as being "on" another component, this includes not only cases where the component is in contact with the other component, but also cases where there is another component between the two components.

[0027] Throughout this specification, the unit "parts by weight" may refer to the proportion of the weight of a component.

[0028] Throughout this specification, the term "(meth)acrylate" is used to refer to both acrylates and methacrylates.

[0029] Throughout this specification, the term "monomer unit" may refer to the form of a monomer that has reacted in the polymer, and more specifically, may refer to the form in which the monomer forms the polymer backbone (e.g., main chain or side chain) through polymerization.

[0030] Throughout this specification, the "weight-average molecular weight" and "number-average molecular weight" of a compound can be calculated using the compound's molecular weight and molecular weight distribution. Specifically, after preparing a sample with a concentration of 1% by weight of the compound by placing tetrahydrofuran (THF) and the compound in a 1 mL glass vial, filtering the standard sample (polystyrene) and the sample through a filter (pore size: 0.45 μm), and injecting them with a GPC syringe, the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample with the calibration curve of the standard sample. An Infinity II 1260 (Agilient) can be used as the measurement device. The flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 °C.

[0031] The contents of this disclosure will be explained in more detail below.

[0032] [Developer solution for photosensitive resin compositions]

[0033] An exemplary embodiment of this disclosure provides a developer solution 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 greater.

[0034] A developer solution for a photosensitive resin composition according to an exemplary embodiment of this disclosure can achieve excellent elongation, sensitivity, and / or adhesion to the substrate and display patterns with improved resolution on the insulating film with high reliability.

[0035] Furthermore, the developer solution used in the photosensitive resin composition can improve safety and environmental pollution issues that arise during the development process, while achieving patterns with excellent mechanical properties and high resolution on the insulating film containing polyimide resin.

[0036] In one exemplary embodiment of this disclosure, the first organic solvent may comprise N,N-diethylformamide (DEF). N,N-diethylformamide (DEF) is used herein as a component that imparts developability to the developer solution used in the photosensitive resin composition. Because the first organic solvent comprises N,N-diethylformamide (DEF), the use of developer solvents designated as hazardous substances, such as N-methyl-2-pyrrolidone (NMP) or cyclopentanone (CPO), can be reduced, and thus safety and environmental pollution issues arising during the development process can be mitigated. Furthermore, because the developer solution comprises the polyimide resin described below, it is particularly suitable for developing processes and patterning methods for insulating films that exhibit excellent elongation, sensitivity, and / or adhesion to the substrate and demonstrate high reliability, allowing for the realization of patterns with excellent physical properties and high resolution on the insulating film.

[0037] In one exemplary embodiment of this disclosure, the photosensitive resin composition may comprise a polyimide resin with an imidization rate of 90% or greater. Specifically, the photosensitive resin composition may be a photosensitive polyimide resin composition, and the imidization rate of the polyimide resin contained in the photosensitive resin composition may be 90% or greater. More specifically, the imidization rate of the polyimide resin may be 90% or greater, 92% or greater, 94% or greater, or 96% or greater, and the resulting insulating film may have excellent elongation, sensitivity, and / or adhesion to the substrate, and exhibit high reliability.

[0038] In one exemplary embodiment of this disclosure, the developer solution for the photosensitive resin composition may be a developer solution for the 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.

[0039] In one exemplary embodiment of this disclosure, the developer solution for the photosensitive resin composition may contain a first organic solvent.

[0040] In one exemplary embodiment of this disclosure, the boiling point of the first organic solvent can be between 160°C and 200°C. Specifically, the boiling point of the first organic solvent can be 165°C or higher, 170°C or higher, or 175°C or higher, and 200°C or lower, 195°C or lower, 190°C or lower, or 185°C or lower. When the first organic solvent has the above-defined boiling point range, it may be more suitable for the development process of polyimide resins, and the developer solution containing it may have a higher developing margin.

[0041] In one exemplary embodiment of this disclosure, the flash point of the first organic solvent can be between 50°C and 90°C. Specifically, the flash point of the first organic solvent can be 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, and 85°C or lower, 80°C or lower, 75°C or lower, or 70°C or lower. When the first organic solvent has the flash point range defined above, it may be more suitable for use in the development process of polyimide resins, and the developer solution containing it may have higher safety.

[0042] In one exemplary embodiment of this disclosure, the content of N,N-diethylformamide can be from 20 parts by weight to 100 parts by weight based on 100 parts by weight of the first organic solvent. Specifically, the content of N,N-diethylformamide based on 100 parts by weight of the first organic solvent can 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, and 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 meets the above-defined ranges, safety and environmental pollution problems that occur during the development process can be mitigated, while achieving patterns with excellent mechanical properties and high resolution on the insulating film containing polyimide resin.

[0043] In one exemplary embodiment of this disclosure, N,N-diethylformamide can be used as the primary solvent in the developer solution for the photosensitive resin composition. In other words, the content of N,N-diethylformamide can be 50 parts by weight or more based on 100 parts by weight of the first organic solvent. When N,N-diethylformamide is used as the primary solvent in the developer solution for the photosensitive resin composition, the resulting pattern can have a higher development tolerance, and significant improvements can be achieved in mitigating safety and environmental pollution issues that arise during the development process.

[0044] In one exemplary embodiment of this disclosure, 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 selected from any of the following: 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 also comprise cyclopentanone (CPO). When the first organic solvent further comprises a polar organic solvent, the resulting pattern may have a higher development tolerance and higher solubility for the photosensitive resin composition may be obtained.

[0045] The polar organic solvent can be any solvent conventionally used in the art, as long as it imparts developability to the developer solution used in the photosensitive resin composition and has solubility in the photosensitive resin composition.

[0046] In other words, the first organic solvent can 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).

[0047] [Photosensitive Resin Composition]

[0048] An exemplary embodiment of this disclosure provides a photosensitive resin composition comprising a polyimide resin, wherein the polyimide resin is the same as described below.

[0049] An exemplary embodiment of the photosensitive resin composition according to this disclosure comprises a polyimide resin and may also comprise a photoacid generator.

[0050] According to an exemplary embodiment of this disclosure, the photoacid generator allows the photosensitive resin composition to act as a chemically amplified composition and can improve pattern resolution, etc., by effectively controlling the acid diffusion length. The photoacid generator can be any conventional photoacid generator without limitation. Specifically, ionic photoacid generators, sulfonyldiazomethane-based photoacid generators, N-sulfonyloxyimide-based photoacid generators, benzoin sulfonate / ester-based photoacid generators, nitrobenzyl sulfonate / ester-based photoacid generators, sulfone-based photoacid generators, oxime-based photoacid generators, triazine-based photoacid generators, etc., can be used.

[0051] In one exemplary embodiment of this disclosure, the photosensitive resin composition may further comprise additives. Specifically, the additives may include at least one of surfactants, antioxidants, and crosslinking agents.

[0052] In one exemplary embodiment of this disclosure, the photosensitive resin composition may include all of the surfactant, antioxidant, and crosslinking agent as additives.

[0053] In one exemplary embodiment of this disclosure, the surfactant may be a silicon-based surfactant or a fluorine-based surfactant. Specifically, the silicon-based surfactant may be BYK-Chemie's BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, and 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., and fluorine-based surfactants can be used for DIC (Dai Nippon Ink &...). Chemicals) 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-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., but not limited to these.

[0054] In one exemplary embodiment of this disclosure, antioxidants can improve the elongation properties of the cured film or its adhesion to metallic materials. Furthermore, antioxidants can inhibit the oxidative degradation of the aliphatic groups or phenolic hydroxyl groups of the polyimide resin and can inhibit metal oxidation by preventing corrosion of the metallic material. Specific examples of antioxidants may include, but are not limited to, the following compounds.

[0055] In one exemplary embodiment of this disclosure, the crosslinking agent is not particularly limited, and any commonly used in the art can be used without limitation. Thermal crosslinking agents or free radical monomers can be used primarily as crosslinking agents. Examples of crosslinking agents include, but are not limited to, compounds having at least two alkoxymethyl groups and / or hydroxymethyl groups and compounds having at least two epoxy groups and / or oxetyl groups. When the compounds exemplified above are used, a crosslinked structure can be formed during firing after patterning by condensation with the resin of this disclosure, and the mechanical properties of the cured resin pattern, such as elongation, can be improved. Furthermore, crosslinking agents can be used in combination of two or more types, allowing for a variety of designs.

[0056] In one exemplary embodiment of this disclosure, specific examples of compounds having at least two alkoxymethyl and / or hydroxymethyl 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, and DML-B isOC-P, DMOM-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, and HMOM-TPHAP (products of Honshu Chemical Industry) and NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (products of Sanwa Chemical) are available from the manufacturers. Two or more of them may also be used.

[0057] In addition, specific examples of compounds having at least two epoxy groups and / or oxetane groups include, but are not limited to, bisphenol A type epoxy resins, bisphenol A type oxetane resins, bisphenol F type epoxy resins, bisphenol F type oxetane resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy-containing organosilicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, you can use EPICLON (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HHP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816 and EPICLON EXA-4822 (products of DainipponInk & Chemicals), RIKARESIN (registered trademark) BEO-60E (product of Shinnihon Rika), EP-4003S and EP-4000S (products of ADEKA), which are available from the manufacturer. You can also use two or more of them.

[0058] In addition, 2-[[4-[2-[4-[1,1-bis[4-(ethylene oxide-2-ylmethoxy)phenyl]ethyl]phenyl]prop-2-yl]phenoxy]methyl]ethylene oxide, tetraethylene glycol dimethacrylate, etc. can be used as crosslinking agents.

[0059] Based on 100 parts by weight of total polyimide resin, the content of crosslinking agent is specifically 0.5 parts by weight or more, more specifically 1 part by weight or more, further more specifically 10 parts by weight or more, and specifically 300 parts by weight or less, or more specifically 200 parts by weight or less, in terms of maintaining mechanical properties such as elongation.

[0060] In one exemplary embodiment of this disclosure, to improve the resolution of the embossed pattern, the photosensitive resin composition may additionally comprise a monomer having photopolymerizable unsaturated bonds. Specifically, the monomer may be a (meth)acrylate compound that participates in free radical polymerization via a photopolymerization initiator. Specific examples include, but are not limited to, monoacrylates or diacrylates of ethylene glycol or polyethylene glycol, and monomethacrylates or dimethacrylates (including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate); monoacrylates or diacrylates of propylene glycol or polypropylene glycol, and monomethacrylates or dimethacrylates; monoacrylates, diacrylates, or triacrylates of glycerol, and monomethacrylates, dimethacrylates, or trimethacrylates; cyclohexane diacrylates and cyclohexane dimethacrylates; diacrylates and dimethacrylates of 1,4-butanediol; diacrylates and dimethacrylates of 1,6-hexanediol; neopentyl glycol. Diacrylates and dimethacrylates of bisphenol A; monoacrylates or diacrylates and monomethacrylates or dimethacrylates of bisphenol A; trimethacrylates; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylates or triacrylates and dimethacrylates or trimethacrylates of glycerol; diacrylates, triacrylates or tetraacrylates of pentaerythritol and dimethacrylates, trimethacrylates or tetramethacrylates of these compounds; ethylene oxide adducts or propylene oxide adducts of these compounds, etc.

[0061] Based on 100 parts by weight of total polyimide resin, the content of monomers having photopolymerizable unsaturated bonds is from 1 part by weight to 50 parts by weight.

[0062] In one exemplary embodiment of this disclosure, the photosensitive resin composition may contain a second organic solvent, and the second organic solvent may contain N,N-diethylformamide (DEF).

[0063] In one exemplary embodiment of this disclosure, the content of N,N-diethylformamide can be from 20 parts by weight to 80 parts by weight based on 100 parts by weight of the second organic solvent. Specifically, the content of N,N-diethylformamide based on 100 parts by weight of the second organic solvent can 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, and 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 meets the above-defined ranges, an insulating film with excellent elongation, sensitivity, and / or adhesion to the substrate and exhibiting high reliability can be achieved.

[0064] In one exemplary embodiment of this disclosure, the second solvent may further comprise a compound known in the art to which this disclosure pertains that is capable of forming a photosensitive resin composition. Specifically, the second solvent may further comprise at least one compound selected from esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0065] Ester-based compounds may include ethyl acetate, n-butyl acetate, isobutyl 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 oxyacetic acid esters (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionic acid esters (e.g., methyl 3-oxypropionic acid, ethyl 3-oxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-propionic acid, ethyl 3-propionic acid)). Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxypropionates (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate or 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-oxobutyrate, ethyl 2-oxobutyrate, etc.

[0066] Ether-based 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, etc.

[0067] Ketone-based compounds can include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0068] Compounds based on aromatic hydrocarbons can include toluene, xylene, anisole, limonene, etc.

[0069] Sulfoxide-based compounds can include dimethyl sulfoxide, etc.

[0070] In one exemplary embodiment of this disclosure, the sensitivity of the photosensitive resin composition can be 350 mJ / cm. 2 Or lower.

[0071] In one exemplary embodiment of this disclosure, the sensitivity of the photosensitive resin composition can be about 350 mJ / cm. 2 Or lower, approximately 340 mJ / cm 2 Or lower, approximately 330 mJ / cm 2 Or lower, approximately 320 mJ / cm 2 Or lower, or about 310 mJ / cm 2 Or lower. There is no particular limit to the lower limit of sensitivity, but if the value is approximately 350 mJ / cm², it is acceptable. 2 If the value is lower, it can be evaluated as a sensing material with excellent physical properties (e.g., micropatterning is easy to form).

[0072] In one exemplary embodiment of this disclosure, based on 100 parts by weight of polyimide resin, the photosensitive resin composition may comprise: 1 to 40 parts by weight of a photoacid generator; 5 to 50 parts by weight of a crosslinking agent; and 0.05 to 5 parts by weight of a surfactant.

[0073] In one exemplary embodiment of this disclosure, the photosensitive resin composition may contain 50 to 500 parts by weight of solvent based on 100 parts by weight of polyimide resin.

[0074] If the above-mentioned components are included in the photosensitive resin composition within the range of the above-defined parts by weight, then even with the use of a small amount of photoacid generator, the sensitivity and physical properties can be improved and the adhesion to the substrate can be improved.

[0075] In one exemplary embodiment of this disclosure, the photosensitive resin composition may be a negative photosensitive resin composition. Specifically, in at least partially exposed photosensitive resin compositions, i.e., in the exposed portions, the precursor contained in the photosensitive resin composition undergoes imidization, and the solubility of the aforementioned developer solution in the photosensitive resin composition may decrease, while the unexposed portions can dissolve in the aforementioned developer solution for the photosensitive resin composition. Therefore, when the photosensitive resin composition is developed using the aforementioned developer solution for the photosensitive resin composition, the unexposed portions dissolve in the developer solution and are removed, while the exposed portions, which have insufficient solubility in the developer solution, can be retained. Specific examples of development methods may include, but are not limited to, shower development, spray development, immersion development, paddle development, etc.

[0076] [Polyimide resin]

[0077] In one exemplary embodiment of this disclosure, the polyimide resin may be a polyimide resin having a structure represented by any of the following chemical formulas 1 to 3.

[0078] [Chemical Formula 1]

[0079]

[0080] [Chemical Formula 2]

[0081]

[0082] [Chemical Formula 3]

[0083]

[0084] In chemical formulas 1 to 3

[0085] For the portion that bonds with other substituents or repeating units,

[0086] L11 can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -SO2-, -CO-, or -OCO-.

[0087] L12 can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted aryl group, -O-, -SO2-, -CO-, or -OCO-.

[0088] R1 and R2 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups.

[0089] R3 and R4 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups.

[0090] r1 and r2 are either the same or different, and are independent integers from 0 to 3, where if r1 is 2 or greater, then R1 is the same or different, and if r2 is 2 or greater, then R2 is the same or different.

[0091] r3 and r4 are either the same or different, and are independent integers from 0 to 4, where r3 is 2 or greater, and r4 ...4 is 2 or greater, and r4 is 2 or greater, and r4 is

[0092] Ra and Rb may be the same or different, and independently represent hydrogen or structures represented by the following chemical formula a.

[0093] [Chemical formula a]

[0094]

[0095] in

[0096] The portion that bonds to chemical formula 1 or chemical formula 2,

[0097] R5 is hydrogen or a substituted or unsubstituted alkyl group, and

[0098] q is an integer from 1 to 10.

[0099] According to one exemplary embodiment of this disclosure, the polyimide resin may contain a structure represented by the above chemical formula 1.

[0100] According to one exemplary embodiment of this disclosure, the polyimide resin may contain a structure represented by the above chemical formula 2.

[0101] According to one exemplary embodiment of this disclosure, the polyimide resin may contain a structure represented by the above chemical formula 3.

[0102] According to an exemplary embodiment of this disclosure, the polyimide resin may comprise a structure represented by chemical formula 1 above and a structure represented by chemical formula 2 above.

[0103] According to an exemplary embodiment of this disclosure, the polyimide resin may include structures represented by chemical formula 1 above and structures represented by chemical formula 3 above.

[0104] According to an exemplary embodiment of this disclosure, the polyimide resin may comprise a structure represented by chemical formula 2 above and a structure represented by chemical formula 3 above.

[0105] According to an exemplary embodiment of this disclosure, the polyimide resin may include a structure represented by chemical formula 1 or chemical formula 3 above, and a structure represented by chemical formula 2 above.

[0106] According to one exemplary embodiment of this disclosure, the polyimide resin may comprise all the structures represented by chemical formulas 1 to 3 above.

[0107] Because the polyimide resin according to an exemplary embodiment of this disclosure comprises flexible chains, includes protecting groups that are insoluble in acids and bases, and can exhibit melting properties at high temperatures, it has the advantages of exhibiting improved elongation, hydrophilicity, and excellent adhesion to substrates. Compared to photosensitive resin compositions using conventional photoinitiators (PIs), photosensitive resin compositions containing polyimide resins facilitate the realization of micropatterns and exhibit higher resolution due to the use of a smaller amount of photoacid generator (PAG) when using PAG. Furthermore, even when using a small amount of PAG, the photosensitive resin compositions according to this disclosure can exhibit excellent sensitivity.

[0108] Specifically, the polyimide resin according to an exemplary embodiment of this disclosure exhibits hydrophilicity due to its inclusion of flexible chains containing ester or ether groups, and demonstrates improved adhesion to substrates due to its melting characteristics at high temperatures (approximately 100°C to 200°C). Furthermore, since the flexible chains provide flexibility to the polyimide resin, elongation is improved and wafer warpage is suppressed. Additionally, the glass transition temperature (Tg) of the polyimide resin is... g This reduces and facilitates the diffusion of photoacid generators contained in the negative photosensitive resin composition, which improves resolution.

[0109] In this instruction manual, It can refer to a portion bonded to another substituent or repeating unit, and can mean a portion bonded to the main chain of the polymer of this disclosure.

[0110] In this specification, the term "polymer" refers to a compound composed of repeating units (basic units). A polymer can refer to a macromolecule or a compound composed of macromolecules.

[0111] Examples of substituents are described below in this specification, but are not limited thereto.

[0112] In this specification, the term "substituted or unsubstituted" means substituted with at least one substituent selected from the group consisting of: deuterium, halogen group, nitrile group, nitro group, hydroxyl group, -COOH group, alkoxy group, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heteroaryl group and heterocyclic group containing at least one of O, N and S atoms, or having no substituent at all.

[0113] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0114] In this specification, the alkoxy group may be straight-chain or branched, and the number of carbon atoms may be 1 to 30, specifically 1 to 20, more specifically 1 to 10, but not particularly limited thereto.

[0115] In this specification, alkyl groups can be straight-chain or branched, and the number of carbon atoms can be from 1 to 60, but are not particularly limited thereto. In one exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. In another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. In yet another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. In this specification, cycloalkyl groups can specifically have 3 to 30 carbon atoms, but are not particularly limited thereto. Cyclopentyl and cyclohexyl groups are used in particular, but are not limited thereto.

[0116] In this specification, alkylene groups are the same as the alkyl groups mentioned above, except that the alkylene groups are divalent.

[0117] In this specification, the cycloalkyl group is not particularly limited, but specifically, it has 3 to 60 carbon atoms. In one exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited thereto.

[0118] In this specification, the alkenyl group can be straight-chain or branched, and it can specifically have 2 to 60 carbon atoms, but is not particularly limited thereto. In one exemplary embodiment, the alkenyl group has 2 to 30 carbon atoms. In another exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. In yet another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. Specific examples of alkenyl groups include, but are not limited to, aryl-substituted alkenyl groups, such as... Matrix, styrene, etc.

[0119] In this specification, there is no particular limitation on the cycloalkenyl group, but the number of carbon atoms can be from 3 to 60. In one exemplary embodiment, the cycloalkenyl group has 3 to 30 carbon atoms. In another exemplary embodiment, the cycloalkenyl group has 3 to 20 carbon atoms. In yet another exemplary embodiment, the cycloalkenyl group has 3 to 6 carbon atoms. Specific examples of cycloalkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl.

[0120] In this specification, the aryl group may specifically have 6 to 60 carbon atoms, but is not particularly limited thereto. In one exemplary embodiment, the aryl group has 6 to 30 carbon atoms. In one exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as phenyl, biphenyl, terphenyl, etc., but is not limited thereto. It may also be a polycyclic aryl group, such as naphthyl, anthracene, indenyl, phenanthrene, pyrene, etc. Benzyl, triphenyl It includes bases, fluorene groups, etc., but is not limited to these.

[0121] In this specification, arylene is the same as the aryl group described above, except that arylene is divalent.

[0122] In this specification, a heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom. It can have 2 to 30, specifically 2 to 20 carbon atoms, but the number of carbon atoms is not particularly limited. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazole, and thiazolyl groups. Azolyl, triazolyl, pyridyl, bipyridyl, triazinyl, acridineyl, pyridazinyl, quinolinyl, isoquinolinyl, indoleyl, carbazoleyl, benzo[] The heterocyclic group includes, but is not limited to, azole, benzimidazol, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, tetrahydropyranyl, etc. Specifically, the heterocyclic group is tetrahydropyranyl.

[0123] In this specification, the above description of heterocyclic groups can be applied to heteroaryl groups, except that heteroaryl groups are aromatic.

[0124] In this specification, the aromatic ring can be aryl or heteroaryl, and the above description applies to both aryl and heteroaryl rings. An aliphatic ring can refer to a ring that is not an aromatic ring.

[0125] In one exemplary embodiment of this disclosure, L11 can be a direct bond, a substituted or unsubstituted C bond. 1-30 Alkylene, substituted or unsubstituted C 6-30 aryl, -SO2-, -CO- or -OCO-.

[0126] In one exemplary embodiment of this disclosure, L11 can be a direct bond, a substituted or unsubstituted C bond. 1-20 Alkylene, substituted or unsubstituted C 6-20 aryl, -SO2-, -CO- or -OCO-.

[0127] In one exemplary embodiment of this disclosure, L11 can be a direct bond, a substituted or unsubstituted C bond. 1-10 Alkylene, substituted or unsubstituted C 6-12 aryl, -SO2-, -CO- or -OCO-.

[0128] In one exemplary embodiment of this disclosure, L11 can be a direct bond, a substituted or unsubstituted C bond. 1-10 Alkylene, -SO2-, -CO-, or -OCO-.

[0129] In one exemplary embodiment of this disclosure, L12 can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted aryl group, -O-, -SO2-, -CO-, or -OCO-.

[0130] In one exemplary embodiment of this disclosure, L12 can be a direct bond, substituted or unsubstituted C. 1-30 Alkylene, substituted or unsubstituted C 6-30 Aryl, -O-, -SO2-, -CO- or -OCO-.

[0131] In one exemplary embodiment of this disclosure, L12 can be a direct bond, substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 6-20 Aryl, -O-, -SO2-, -CO- or -OCO-.

[0132] In one exemplary embodiment of this disclosure, L12 can be a direct bond, substituted or unsubstituted C. 1-10 Alkylene, substituted or unsubstituted C 6-12 Aryl, -O-, -SO2-, -CO- or -OCO-.

[0133] In one exemplary embodiment of this disclosure, L12 can be a direct bond, substituted or unsubstituted C. 1-10 Alkylene, or -O-.

[0134] In one exemplary embodiment of this disclosure, R1 and R2 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0135] In one exemplary embodiment of this disclosure, R1 and R2 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0136] In one exemplary embodiment of this disclosure, R1 and R2 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0137] In one exemplary embodiment of this disclosure, R3 and R4 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0138] In one exemplary embodiment of this disclosure, R3 and R4 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0139] In one exemplary embodiment of this disclosure, R3 and R4 may be the same or different, and may independently be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0140] In one exemplary embodiment of this disclosure, Ra and Rb may be the same or different, and are independently hydrogen or structures represented by the following chemical formula a.

[0141] [Chemical formula a]

[0142]

[0143] In one exemplary embodiment of this disclosure, chemical formula a can be any of the following structures, but is not limited thereto, and q can be any integer from 1 to 10.

[0144]

[0145] In one exemplary embodiment of this disclosure, R5 can be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0146] In one exemplary embodiment of this disclosure, R5 can be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0147] In one exemplary embodiment of this disclosure, R5 can be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0148] In one exemplary embodiment of this disclosure, at least one of Ra and Rb may include 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 100 mol% or less, based on the total content of the polyimide resin.

[0149] In one exemplary embodiment of this disclosure, at least one of Ra and Rb may include a structure represented by chemical formula a, and based on the total content of the polyimide resin, the content of the structure represented by chemical formula a may be 10 mol% or more and 100 mol% or less, 20 mol% or more and 100 mol% or less, 30 mol% or more and 100 mol% or less, 40 mol% or more and 100 mol% or less, 50 mol% or more and 100 mol% or less, 60 mol% or more and 100 mol% or less, 70 mol% or more and 100 mol% or less, 80 mol% or more and 100 mol% or less, 90 mol% or more and 100 mol% or less, or 100%.

[0150] In one exemplary embodiment of this disclosure, the total content of the polyimide resin, represented by the structure of formula a, can be determined by commercially available NMR. Furthermore, after the resin synthesis reaction is complete, the amount of OH prior to the reaction is obtained from the number of protons in all aromatic rings of the polyimide, and then the content (mol%) of the structure represented by formula a can be determined by the number of protons in formula a (the integral of the peaks at 6.41 ppm to 5.83 ppm (3H)) relative to the amount of OH prior to the reaction.

[0151] In one exemplary embodiment of this disclosure, each of chemical formulas 1 to 3 may be represented by any of the following structures.

[0152]

[0153]

[0154]

[0155] In the structural formula, Ra and Rb are the same as those defined in chemical formulas 1 and 2, and It can be a portion that is bonded to other substituents or repeating units.

[0156] In one exemplary embodiment of this disclosure, the polyimide resin may also comprise a structure represented by the following chemical formula E-1 or chemical formula E-2.

[0157] [Chemical Formula E-1]

[0158]

[0159] [Chemical formula E-2]

[0160]

[0161] In chemical formulas E-1 and E-2,

[0162] For the portion that bonds with other substituents or repeating units,

[0163] Re1 is hydrogen or a substituted or unsubstituted alkyl group.

[0164] re1 is an integer from 0 to 4, where when re1 is 2 or greater, two or more re1 values ​​are the same or different.

[0165] Re represents hydrogen or a structure represented by the chemical formula a.

[0166] In one exemplary embodiment of this disclosure, the structure represented by chemical formula E-1 or chemical formula E-2 can be an end group of a polyimide resin.

[0167] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0168] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0169] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0170] In one exemplary embodiment of this disclosure, Re can be hydrogen or a structure represented by the chemical formula a.

[0171] In one exemplary embodiment of this disclosure, Re is a structure represented by chemical formula a. The content of chemical formula a is the same as described above.

[0172] In one exemplary embodiment of this disclosure, the polyimide resin may also include a structure represented by the chemical formula E-2 as an end group.

[0173] [Chemical formula E-2]

[0174]

[0175] In chemical formula E-2,

[0176] For the portion that bonds with other substituents or repeating units,

[0177] Re1 is hydrogen or a substituted or unsubstituted alkyl group.

[0178] re1 is an integer from 0 to 4, where when re1 is 2 or greater, two or more re1 values ​​are the same or different.

[0179] Re represents hydrogen or a structure represented by the chemical formula a.

[0180] In one exemplary embodiment of this disclosure, the polyimide resin may also comprise a structure represented by any one of the following chemical formulas 4-1 to 4-4.

[0181] [Chemical Formula 4-1]

[0182]

[0183] [Chemical Formula 4-2]

[0184]

[0185] [Chemical Formula 4-3]

[0186]

[0187] [Chemical Formula 4-4]

[0188]

[0189] In chemical formulas 4-1 to 4-4,

[0190] For the portion that bonds with other substituents or repeating units,

[0191] L21 to L23 may be the same or different, and are independently a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted aryl group, -O-, -CO-, -S-, -COO-L'-OCO-, or -O-(L) m -O-,

[0192] L' and L'' may be the same or different, and are independently substituted or unsubstituted alkylene or substituted or unsubstituted arylene.

[0193] m is an integer from 1 to 5, where if m is 2 or greater, then L" is the same or different.

[0194] Ra1 to Ra6 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups.

[0195] Ra1 through Ra6 are each identical or different, and are independent integers from 0 to 3, wherein if Ra1 is 2 or greater, then Ra1 is identical or different; if Ra2 is 2 or greater, then Ra2 is identical or different; if Ra3 is 2 or greater, then Ra3 is identical or different; if Ra4 is 2 or greater, then Ra4 is identical or different; if Ra5 is 2 or greater, then Ra5 is identical or different; and if Ra6 is 2 or greater, then Ra6 is identical or different.

[0196] Cy is a substituted or unsubstituted aliphatic or aromatic ring.

[0197] In one exemplary embodiment of this disclosure, L21 to L23 may each be the same or different, and are independently direct bonds, substituted or unsubstituted C. 1-30 Alkylene, substituted or unsubstituted C 6-30 aryl, -SO2-, -CO- or -OCO-.

[0198] In one exemplary embodiment of this disclosure, L21 to L23 may each be the same or different, and are independently direct bonds, substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 6-20 aryl, -SO2-, -CO- or -OCO-.

[0199] In one exemplary embodiment of this disclosure, L21 to L23 may each be the same or different, and are independently direct bonds, substituted or unsubstituted C. 1-10 Alkylene, substituted or unsubstituted C 6-12 aryl, -SO2-, -CO- or -OCO-.

[0200] In one exemplary embodiment of this disclosure, Ra1 to Ra6 may each be the same or different, and are independently hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0201] In one exemplary embodiment of this disclosure, Ra1 to Ra6 may each be the same or different, and are independently hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0202] In one exemplary embodiment of this disclosure, Ra1 to Ra6 may each be the same or different, and are independently hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0203] In one exemplary embodiment of this disclosure, the structure represented by any of chemical formulas 4-1 to 4-4 may be derived from any of the following chemical formulas.

[0204]

[0205]

[0206] In one exemplary embodiment of this disclosure, the weight-average molecular weight of the polyimide resin can be from 3,000 g / mol to 70,000 g / mol. Specifically, the weight-average molecular weight of the polyimide resin can be in the range of 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 may exhibit reduced adhesion. Furthermore, if the weight-average molecular weight of the polyimide resin exceeds 70,000 g / mol, development may be impeded due to reduced sensitivity, or residues (e.g., scum) may undesirably remain on the insulating film.

[0207] [Methods for developing photosensitive resin compositions and methods for pattern formation]

[0208] An exemplary embodiment of this disclosure provides a development method comprising the step of developing a photosensitive resin composition at least partially exposed to light using the aforementioned developer solution.

[0209] Furthermore, an exemplary embodiment of this disclosure provides a pattern forming method comprising the steps of: providing an insulating film comprising a photosensitive resin composition or a cured product thereof; selectively exposing the insulating film to light; and developing the exposed insulating film with the aforementioned developing agent solution.

[0210] Each step will be explained below.

[0211] According to an exemplary embodiment of this disclosure, the step of providing an insulating film can be performed by applying a photosensitive resin composition to the surface of the object to be coated, followed by curing.

[0212] While there are no specific limitations on the method used to apply the photosensitive resin composition, spraying, roller coating, spin coating, etc., can be used. Spin coating is generally widely used. Furthermore, after film formation, residual solvents can be partially removed under reduced pressure if necessary.

[0213] Specific examples of a light source for curing a photosensitive resin composition according to an exemplary embodiment of this disclosure may include, but are not limited to, a mercury vapor arc, a carbon arc, an Xe arc, etc., that emit light with wavelengths from 250 nm to 450 nm.

[0214] If necessary, the insulating film can be heat-treated after the photosensitive resin composition has been cured.

[0215] Heat treatment can be carried out using heating devices such as hot plates, hot air circulators, infrared furnaces, etc., and can be performed at 180°C to 250°C or 190°C to 220°C.

[0216] According to an exemplary embodiment of this disclosure, the step of selectively exposing an insulating film to light can be performed by selectively exposing the resulting insulating film to light in a desired pattern. Such selective exposure can typically be performed using a mask that includes the desired pattern.

[0217] Exposure can be achieved using ultraviolet light, electron beams, or laser beams emitted by low-pressure mercury lamps, high-pressure mercury lamps, g-line steppers, i-line steppers, etc. Furthermore, the exposure dose can be controlled based on the light source used for exposure or the thickness of the coated film, but it is typically 1 mJ / cm². 2 Up to 1000 mJ / cm 2 Specifically, 10 mJ / cm 2Up to 500 mJ / cm 2 .

[0218] According to an exemplary embodiment of this disclosure, the step of developing the exposed insulating film with the aforementioned developing solution can be performed by developing the insulating film selectively exposed with a desired pattern using the developing solution. In this way, unexposed portions can be dissolved in the developing solution of the photosensitive resin composition and removed from the selectively exposed insulating film.

[0219] [Insulating film]

[0220] An exemplary embodiment of this disclosure provides an insulating film comprising the above-described photosensitive resin composition or a cured product thereof.

[0221] The insulating film may contain the photosensitive resin composition as is.

[0222] The insulating film may contain a cured product of a photosensitive resin composition.

[0223] Because insulating films exhibit excellent chemical resistance and mechanical properties, they can be specifically used as insulating films for semiconductor devices, interlayer insulating films for redistribution layers, etc. Furthermore, insulating films can be used as photoresists, photoresists, top solder resists, etc.

[0224] The insulating film may include a support or a substrate.

[0225] There are no specific limitations on the support or substrate, and it can be any support or substrate known in the art. For example, a substrate for electronic components, a substrate on which a specific wiring pattern is formed, etc., can be used. The substrate can be, for example, silicon; silicon nitride; a metal substrate such as titanium, tantalum, palladium, tungsten titanate, copper, chromium, iron, aluminum, gold, nickel, etc.; a glass plate; etc. The wiring pattern can be made of, for example, copper, solder, chromium, aluminum, nickel, gold, etc., but is not limited thereto. Specifically, the support or substrate can be a silicon wafer.

[0226] In one exemplary embodiment of this disclosure, the thickness of the insulating film can be from 1 μm to 100 μm. If the thickness of the insulating film meets the range defined above, the insulating film can have the excellent chemical resistance and mechanical properties contemplated in this specification. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0227] [Semiconductor Devices]

[0228] An exemplary embodiment of this disclosure provides a semiconductor device including an insulating film.

[0229] In addition to the insulating film, the semiconductor device may also include various components commonly used in the art.

[0230] The present disclosure is described in detail below by way of examples. However, embodiments of the present disclosure may be modified in several different ways, and the scope of the present disclosure is not to be construed as limited to the embodiments described below. The embodiments of this specification are provided to describe the present disclosure more fully to those skilled in the art.

[0231] Invention Embodiments

[0232] Aggregate Examples

[0233] Polymerization Example 1

[0234] Under a nitrogen atmosphere, 0.8 equivalents of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA) and 0.2 equivalents of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (bis-APAF) were dissolved in diethylformamide (DEF), and then heated to 80°C with stirring to ensure complete dissolution. Next, 4,4'-oxophthalic anhydride (ODPA) and 5-norbornene-2,3-dicarboxylic anhydride (NDA) were introduced, a Dean-Stark separator was connected, and the reaction was allowed to proceed for 6 hours. The reaction mixture was then heated to 150°C and allowed to proceed overnight. The residual monomers and cyclization rate were determined by NMR, and the polymerization solution was obtained by terminating the reaction. The resulting polymerization solution was then diluted with tetrahydrofuran (THF) and precipitated in methanol (MeOH), followed by drying to obtain the solid contents of polymer 1. The molecular weight of polymer 1 was measured by gel permeation chromatography (GPC), and the weight-average molecular weight was determined to be 35,000 g / mol. Furthermore, the glass transition temperature (Tg) of polymer 1, determined by differential scanning calorimetry (DSC), was 245 °C.

[0235] [Polymer 1]

[0236]

[0237] In polymer 1,

[0238] q is a value that makes the weight-average molecular weight of the polymer 35,000 g / mol.

[0239] And q is an integer from 5 to 40.

[0240] Synthesis example 1

[0241] After adding 0.016 equivalents of triethylamine based on the OH of polyimide and 0.1 equivalents of 2-acryloyloxyethyl isocyanate to polymer 1 prepared in polymerization example 1, an oil bath was set up and the reaction was carried out overnight at 60°C. Then, the reaction was terminated after the disappearance of the 2H peak of 2-acryloyloxyethyl isocyanate (AOI) at 4.25 ppm was confirmed by NMR.

[0242] The total amount of OH groups in polymer 1 was calculated by comparing the total area of ​​aromatic rings appearing at 7 ppm or greater on NMR with the input amount, and the substitution ratio via AOI was determined based on the total OH groups by the area of ​​the peak (3H) appearing at approximately 6 ppm. This showed that the polymer was substituted via AOI at 10 mol%. The molecular weight of the polymer was measured by gel permeation chromatography (GPC), and the weight-average molecular weight was determined to be 19,000 g / mol. Furthermore, the glass transition temperature (Tg) of the polymer, determined by differential scanning calorimetry (DSC), was 260 °C.

[0243] The structure of the polymer prepared in Synthesis Example 1 is as follows.

[0244] [Polymer of Synthetic Example 1]

[0245]

[0246] In the polymer of Synthetic Example 1,

[0247] q is a value that makes the weight-average molecular weight of the polymer 36,000 g / mol.

[0248] And q is an integer from 5 to 40.

[0249] Preparation Example

[0250] Preparation Example 1 - Preparation of Photosensitive Resin Composition

[0251] A photosensitive resin according to Synthesis Example 1 was prepared. Then, based on 100 parts by weight of the above-mentioned photosensitive resin, 8.4 parts by weight of RP-1040 (Nippon Kayaku Co. Ltd.) as a crosslinking agent, 0.4 parts by weight of TCL-005 (LGCCo.), 1.85 parts by weight of OXE-04 (BASF Co.) as a free radical photoinitiator, and additives including 0.18 parts by weight of KBM503 (Shin-etsu Co.) as a coupling agent and 0.02 parts by weight of BYK-307 (BYK Chemie Co.) as a surfactant were introduced into 60 parts by weight of a second organic solvent containing N,N-diethylformamide (DEF) and γ-butyrolactone (GBL) mixed in a 55:5 weight ratio, thereby providing a photosensitive resin composition. Here, the solids content of the photosensitive resin composition is 39.00% by weight.

[0252] Preparation Example 2-1: Preparation of Polyimide Film

[0253] The polyimide film of Preparation Example 2-1 was obtained by curing the photosensitive resin composition of Preparation Example 1 under the following conditions. Specifically, the photosensitive resin composition was coated onto a Si wafer substrate to a thickness of 10 μm by spin coating and subjected to soft baking on a hot plate set to 90°C to 130°C. Then, it was exposed to light at a dose of 400 mJ to 900 mJ using an i-line stepper lithography machine (365 nm) as the light source and post-baked in an oven set to 160°C to 230°C under a nitrogen atmosphere for 20 to 240 minutes, thereby providing the polyimide film.

[0254] Preparation Example 2-2: Preparation of Polyimide Film

[0255] The polyimide film of Preparation Example 2-2 was obtained in the same manner as the polyimide film of Preparation Example 2-1, except that the photosensitive resin composition of Preparation Example 1 was coated onto the Si wafer substrate to a thickness of 11.5 μm by spin coating.

[0256] Resolution evaluation

[0257] Example 1-1

[0258] A polyimide film was prepared according to Preparation Example 2-1. Next, the polyimide film was exposed to light using an 8.0 μm (1:1.5 pitch) patterned mask, and development was repeated twice for 30 seconds using a developer solution containing 100% by weight N,N-diethylformamide (DEF) as the first organic solvent (spray PGMEA rinse for 20 to 180 seconds).

[0259] Then, optical microscopy (OM) was used to determine the top critical dimension (top CD) of the patterned surface, and scanning electron microscopy (SEM) was used to determine the bottom critical dimension (hole CD) of the hole. Furthermore, the dimensions of the patterned mask were compared with the dimensions of the resulting holes to evaluate the resolution. The evaluation results are shown in… Figure 1 And in Table 1.

[0260] Examples 1-2

[0261] Resolution was evaluated in the same manner as in Examples 1-1, except that the polyimide film was exposed to light using a 10.0 μm (1:1.5 pitch) patterned mask. The evaluation results are shown in... Figure 2 And in Table 1.

[0262] Examples 1-3

[0263] Resolution was evaluated in the same manner as in Examples 1-1, except that the polyimide film was exposed to light using a 15.0 μm (1:1.5 pitch) patterned mask. The evaluation results are shown in... Figure 3 And in Table 1.

[0264] Comparative Example 1-1

[0265] Resolution was evaluated in the same manner as in Examples 1-1, except that 100% by weight of cyclopentanone (CPO) was used as the developer solution. The evaluation results are shown below. Figure 1 And in Table 1.

[0266] Comparative Examples 1-2

[0267] Resolution was evaluated in the same manner as in Examples 1-2, except that 100% by weight cyclopentanone (CPO) was used as the developer solution. The evaluation results are shown below. Figure 4 And in Table 1.

[0268] Comparative Examples 1-3

[0269] Resolution was evaluated in the same manner as in Examples 1-2, except that 100% by weight cyclopentanone (CPO) was used as the developer solution. The evaluation results are shown below. Figure 5 And in Table 1.

[0270] [Table 1]

[0271]

[0272] Figure 1Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Examples 1-1 and Comparative Examples 1-1 are shown. Figure 2 and Figure 3 Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Examples 1-2 and 1-3 are shown. Figure 4 and Figure 5 Images illustrating the results of evaluating the resolution of the developer solutions for the photosensitive resin compositions according to each of Comparative Examples 1-2 and 1-3 are shown. Specifically, Figure 1 (a) is a scanning electron microscope (SEM) side image showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to Examples 1-1, and Figure 1 (b) is a SEM side image showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to Comparative Example 1-1. Meanwhile, Figures 2 to 5 (a) of each is an optical microscope (OM) image showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to each of Examples 1-2, Examples 1-3, Comparative Examples 1-2 and 1-3. Figures 2 to 5 (b) of each is a SEM side image showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to each of Examples 1-2, Examples 1-3, Comparative Examples 1-2 and Comparative Examples 1-3, and Figures 2 to 5 (c) of each of them is a top-view SEM image showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to each of Examples 1-2, Examples 1-3, Comparative Examples 1-2 and Comparative Examples 1-3.

[0273] Refer to Table 1 and Figure 1 After evaluating the resolution of each of Examples 1-1 and Comparative Examples 1-1, a similarity ratio of the top CD to the hole CD (i.e., the value of the diameter of the pattern surface relative to the diameter of the bottom portion of the hole) was obtained (1.2), and thus it was determined that the two embodiments have equivalent or improved resolution levels.

[0274] Simultaneously, the size of the formed pattern can be determined by either OM (Optical Membrane) or SEM (Sequencing Electron) images. However, because OM offers low accuracy due to its resolution and limited magnification, the shape of the formed pores, the spots on the cured film, and the formation of residues are determined by OM images, and then the precise size of the pores is determined using SEM images. Refer to Table 1 and... Figures 2 to 5In each of the examples (a), when evaluating the resolution of Examples 1-2 or 1-3 using DEF as the developer solution, the resulting holes had better shapes and no spots or residues were produced compared to the resolution evaluation of Comparative Examples 1-2 or 1-3 using CPO as the developer solution. This indicates that Examples 1-2 and 1-3 have an equivalent level of high reliability.

[0275] Meanwhile, refer to Table 1 and Figures 2 to 5 In each of (b) and (c), in the case of evaluating the resolution of Examples 1-2 or 1-3 using DEF as the developer solution, compared with the results of evaluating the resolution of Comparative Examples 1-2 or 1-3 using CPO as the developer solution, a similarity ratio of the top CD to the hole CD (i.e., the value of the diameter of the pattern surface relative to the diameter of the bottom portion of the hole) was obtained, and the shape of the formed hole was better.

[0276] As can be seen from the above results, the developer solution for the photosensitive resin composition according to an exemplary embodiment of the present disclosure can achieve high-resolution patterns while exhibiting excellent safety due to its high flash point and low volatility.

[0277] Example 2-1

[0278] Polyimide films were prepared according to Preparation Example 2-2. Next, the resolution was evaluated in the same manner as in Example 1-1, except that development was repeated twice for 50 seconds using a developer solution containing 100% by weight N,N-diethylformamide (DEF) as the first organic solvent (spray PGMEA rinsing for 20 to 180 seconds). The results are shown in… Figure 6 And in Table 2.

[0279] Furthermore, the minimum achieved resolution was evaluated as a factor in assessing the resolution. The results are shown in Table 2. Specifically, although exposure and development were performed in the same manner as in Examples 1-1, the difference was the use of different patterned masks to determine the minimum achieved resolution, i.e., the minimum aperture critical size (aperture CD), that enables the formation of a uniform aperture pattern.

[0280] Example 2-2

[0281] Resolution was evaluated in the same manner as in Examples 2-1, except that a mixture of 50 wt% N,N-diethylformamide (DEF) and 50 wt% cyclopentanone (CPO) was used as the developer solution. The results are shown in... Figure 7 And in Table 2.

[0282] Example 2-3

[0283] Resolution was evaluated in the same manner as in Examples 2-1, except that a mixture of 20 wt% N,N-diethylformamide (DEF) and 50 wt% cyclopentanone (CPO) was used as the developer solution. Results are shown in... Figure 8 And in Table 2.

[0284] Examples 2-4

[0285] Resolution was evaluated in the same manner as in Examples 2-1, except that a mixture of 10 wt% N,N-diethylformamide (DEF) and 90 wt% cyclopentanone (CPO) was used as the developer solution. The results are shown in... Figure 9 And in Table 2.

[0286] Comparative Example 2-1

[0287] Resolution was evaluated in the same manner as in Examples 2-1, except that 100% by weight cyclopentanone (CPO) was used as the developer solution. The results are shown in... Figure 10 And in Table 2.

[0288] [Table 2]

[0289]

[0290] Figures 6 to 9 Images illustrating the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to each of Examples 2-1 to 2-4 are shown. Figure 10 These are images showing the results of evaluating the resolution of the developer solution for the photosensitive resin composition according to Comparative Example 2-1. Refer to Table 2 and... Figures 6 to 10 After evaluating the resolution of each of Examples 2-1 to 2-4 and Comparative Example 2-1, it can be seen that a similarity ratio (1.2 or less) between the top CD and the hole CD (i.e., the value of the diameter of the patterned surface relative to the diameter of the bottom portion of the hole) was obtained, thus determining that these examples have an equivalent or improved level of resolution. Specifically, as the proportion of DEF in the developer solution increases, the value of the hole CD increases even though the value of the top CD is similar. This indicates that as the proportion of DEF in the developer solution increases, the ratio of the top CD to the hole CD (i.e., the value of the diameter of the patterned surface relative to the diameter of the bottom portion of the hole) decreases, resulting in improved resolution.

[0291] Specifically, refer to Figures 6 to 8In Examples 2-1 to 2-3, where the DEF content in the developer solution was 20% by weight or greater, it was observed that the formed apertures had better shapes, and the ratio of the top CD to the aperture CD (i.e., the diameter of the patterned surface relative to the diameter of the aperture bottom portion) improved to 1.0 or 1.1. Specifically, it was observed that the aperture CD value increased with increasing DEF proportion, thereby providing a trend that facilitated the realization of micropatterns. Furthermore, in Examples 2-1 to 2-3, the minimum achieved resolution was 8 μm, which further facilitated the realization of micropatterns.

[0292] In addition, refer to Figure 6 and Figure 7 Compared to other examples that did not use DEF as the primary solvent, Examples 2-1 and 2-2, which used 50% by weight or more DEF as the primary solvent for the developer solution, provided better resolution evaluation results and showed a greater effect in improving issues related to safety and environmental pollution.

[0293] As can be seen from the foregoing, a developer solution for a photosensitive resin composition according to an exemplary embodiment of the present disclosure can achieve patterns with high resolution while exhibiting excellent safety due to its high flash point and low volatility.

[0294] In other words, a developer solution for a photosensitive resin composition according to an exemplary embodiment of this disclosure can achieve excellent elongation, sensitivity, and / or adhesion to the substrate and display patterns with improved resolution on the insulating film with high reliability.

[0295] Furthermore, the developer solution used in the photosensitive resin composition can improve safety and environmental pollution issues that arise during the development process, while achieving patterns with excellent mechanical properties and high resolution on the insulating film containing polyimide resin.

[0296] The foregoing detailed description illustrates and describes this disclosure. Furthermore, the foregoing description merely illustrates and describes specific exemplary embodiments of this disclosure. As mentioned above, this disclosure can be used in various different combinations, modifications, and environments, and can be changed or modified within the scope of the concept of this disclosure described in this specification, within the scope equivalent to that described in this specification, and / or within the scope of technology or knowledge in related fields. Therefore, the detailed description of this disclosure is not intended to limit this disclosure to the specific exemplary embodiments. Moreover, the appended claims should be construed as including other embodiments.

[0297] [Explanation of reference numerals in the attached figures]

[0298] Top CD: Diameter of the patterned surface

[0299] Hole CD: Diameter of the bottom portion of the hole

Claims

1. A developer solution for a photosensitive resin composition, comprising a first organic solvent, 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 greater.

2. The developer solution for a photosensitive resin composition according to claim 1, wherein the content of N,N-diethylformamide is from 20 parts by weight to 100 parts by weight based on 100 parts by weight of the first organic solvent.

3. The developer solution for a photosensitive resin composition according to claim 1, wherein the first organic solvent further comprises a mixture selected from any one of the following: 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 developer solution for a photosensitive resin composition according to claim 1, wherein the polyimide resin is a polyimide resin comprising a structure represented by any one of the following chemical formulas 1 to 3: [Chemical Formula 1] ， [Chemical Formula 2] ， [Chemical Formula 3] ， In chemical formulas 1 to 3 For the portion that bonds with other substituents or repeating units, L11 can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -SO2-, -CO-, or -OCO-. L12 can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted aryl group, -O-, -SO2-, -CO-, or -OCO-. R1 and R2 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups. R3 and R4 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups. r1 and r2 are either the same or different, and are independent integers from 0 to 3, where if r1 is 2 or greater, then R1 is the same or different, and if r2 is 2 or greater, then R2 is the same or different. r3 and r4 are either the same or different, and are independent integers from 0 to 4, where r3 is 2 or greater, and r4 ...4 is 2 or greater, and r4 is 2 or greater, and r4 is Ra and Rb may be the same or different, and independently represent hydrogen or structures represented by the following chemical formula a. [Chemical formula a] ， In chemical formula a, The portion that bonds to chemical formula 1 or chemical formula 2, R5 is hydrogen or a substituted or unsubstituted alkyl group, and q is an integer from 1 to 10.

5. The developer solution for a 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: [Chemical formula E-2] ， In chemical formula E-2, For the portion that bonds with other substituents or repeating units, Re1 is hydrogen or a substituted or unsubstituted alkyl group. re1 is an integer from 0 to 4, where when re1 is 2 or greater, two or more re1 values ​​are the same or different. Re represents hydrogen or a structure represented by the chemical formula a.

6. The developer solution for a photosensitive resin composition according to claim 4, wherein the polyimide resin further comprises a structure represented by any one of the following chemical formulas 4-1 to 4-4: [Chemical Formula 4-1] ， [Chemical Formula 4-2] ， [Chemical Formula 4-3] ， [Chemical Formula 4-4] ， In chemical formulas 4-1 to 4-4, For the portion that bonds with other substituents or repeating units, L21 to L23 may be the same or different, and are independently a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted aryl group, -O-, -CO-, -S-, -COO-L'-OCO-, or -O-(L) m -O-, L' and L'' may be the same or different, and are independently substituted or unsubstituted alkylene or substituted or unsubstituted arylene. m is an integer from 1 to 5, where if m is 2 or greater, then L" is the same or different. Ra1 to Ra6 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups. Ra1 through Ra6 are each identical or different, and are independent integers from 0 to 3, wherein if Ra1 is 2 or greater, then Ra1 is identical or different; if Ra2 is 2 or greater, then Ra2 is identical or different; if Ra3 is 2 or greater, then Ra3 is identical or different; if Ra4 is 2 or greater, then Ra4 is identical or different; if Ra5 is 2 or greater, then Ra5 is identical or different; and if Ra6 is 2 or greater, then Ra6 is identical or different. Cy is a substituted or unsubstituted aliphatic or aromatic ring.

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

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

9. The developer solution for a photosensitive resin composition according to claim 8, wherein the content of N,N-diethylformamide is from 20 to 80 parts by weight based on 100 parts by weight of the second organic solvent.

10. A developing method comprising the step of developing a photosensitive resin composition at least partially exposed to light using a developing agent solution for a photosensitive resin composition according to claim 1.

11. A method for forming a pattern, comprising the following steps: Provides an insulating film comprising a photosensitive resin composition or a cured product thereof; The insulating film is selectively exposed to light; as well as The exposed insulating film is developed using the developer solution for the photosensitive resin composition according to claim 1.

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