Photosensitive resin composition, insulating film, and semiconductor device

Abstract

The present disclosure aims to provide a photosensitive resin composition containing a polyimide resin, an insulating film, and a semiconductor device.

Description

Technical Field

[0001] This disclosure relates to photosensitive resin compositions, insulating films, and semiconductor devices. Specifically, it relates to photosensitive resin compositions, insulating films, and semiconductor devices comprising polyimide resins. This application claims the benefit of Korean Patent Application No. 10-2023-0123315, filed with the Korean Intellectual Property Office on September 15, 2023, 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] As miniaturization technology expands its application in FAB (fabrication) processes, packaging technology is also undergoing significant changes to manufacture 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 (PSPI) for redistribution layers (RDLs) is increasing significantly. PSPIs can be cured at low temperatures and have excellent physical properties.

[0005] Negative photosensitive polyimides possess relatively good mechanical properties, but achieving high resolution is difficult. While positive photosensitive polyimides can achieve relatively high resolution, obtaining satisfactory mechanical properties is challenging.

[0006] Therefore, it is necessary to develop photosensitive polyimide materials that satisfy both high resolution and mechanical properties.

[0007] Specifically, there is a need to develop methods for deriving and evaluating factors that have a major impact on the reliability of insulating films made from photosensitive polyimides. For example, there is a need to develop high-reliability photosensitive resin compositions for use in semiconductor devices manufactured through thermal cycling (TC) testing, and insulating films containing them. Summary of the Invention

[0008] Technical issues

[0009] This disclosure aims to provide photosensitive resin compositions, insulating films, and semiconductor devices comprising polyimide resins.

[0010] However, the problems to be solved 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 photosensitive resin composition comprising a polyimide resin, wherein, when the photosensitive resin composition is cured to prepare a film with a thickness of 10 μm and the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film are measured, I, as defined by Equation 1, TC Value 1000 or greater:

[0013] [Equation 1]

[0014]

[0015] Among them I TC For the thermal cycling index of the membrane,

[0016] Y is the Young's modulus of the membrane.

[0017] T is the tensile strength of the membrane.

[0018] E is the elongation at break of the membrane.

[0019] C is the coefficient of thermal expansion of the film, and

[0020] C Cu is the coefficient of thermal expansion of copper.

[0021] An exemplary embodiment of this disclosure provides an insulating film comprising the photosensitive resin composition or a cured product thereof.

[0022] An exemplary embodiment of this disclosure provides a semiconductor device that includes the insulating film.

[0023] Beneficial effects

[0024] A photosensitive resin composition according to an exemplary embodiment of this disclosure can form an insulating film with excellent elongation, sensitivity and / or adhesion to a substrate, and a highly reliable insulating film can be formed in a simpler manner by measuring specific physical properties of the film sample and evaluating evaluation factors.

[0025] A photosensitive resin composition according to an exemplary embodiment of the present disclosure can exhibit excellent mechanical properties (e.g., high elongation and substrate adhesion, low sensitivity, etc.) as a photosensitive material, and can form micropatterns without modification by crosslinkable polymers.

[0026] Since the insulating film and semiconductor device according to an exemplary embodiment of the present disclosure comprise a photosensitive resin composition having high elongation, low sensitivity and excellent adhesion to the substrate, they can have high reliability by preventing wafer warping in the semiconductor device using the insulating film.

[0027] The beneficial effects of this disclosure are not limited to those described above, and those skilled in the art can clearly understand from this specification and the accompanying drawings the effects not mentioned. Detailed Implementation

[0028] Throughout this specification, unless the context clearly states otherwise, when a part is described as "containing" a component, this does not preclude the presence of other components, but rather means that other components may be included.

[0029] 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.

[0030] Throughout this specification, the unit "parts by weight" may refer to the proportion of the weight of a component.

[0031] Throughout this specification, the term "(meth)acrylate" is used to refer to both acrylates and methacrylates.

[0032] Throughout this specification, the term "monomer unit" may refer to the form of a monomer in a polymer, and more specifically, to the form in which the monomer forms the polymer backbone (e.g., main chain or side chain) through polymerization.

[0033] 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 1% by weight sample 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.

[0034] An exemplary embodiment of this disclosure provides a photosensitive resin composition comprising a polyimide resin, wherein, when the photosensitive resin composition is cured to prepare a film with a thickness of 10 μm and the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film are measured, I, as defined by Equation 1, TC The value is 1000 or greater.

[0035] [Equation 1]

[0036]

[0037] In equation 1,

[0038] I TC For the thermal cycling index of the membrane,

[0039] Y is the Young's modulus of the membrane.

[0040] T is the tensile strength of the membrane.

[0041] E is the elongation at break of the membrane.

[0042] C is the coefficient of thermal expansion of the film, and

[0043] C Cu is the coefficient of thermal expansion of copper.

[0044] A photosensitive resin composition according to an exemplary embodiment of this disclosure can form an insulating film with excellent elongation, sensitivity and / or adhesion to a substrate, and a highly reliable insulating film can be formed in a simpler manner by measuring specific physical properties of the film sample and evaluating evaluation factors.

[0045] The measured values ​​of the physical properties in Equation 1 above can be determined by the composition of the photosensitive resin composition, curing conditions, etc.

[0046] The methods for measuring the physical properties of film samples of photosensitive resin compositions and obtaining evaluation factors will be described in more detail below.

[0047] [Methods for measuring physical properties and deriving evaluation factors]

[0048] A photosensitive resin composition comprising a polyimide resin according to an exemplary embodiment of this disclosure may have a thermal cycling index of 1000 or greater (I0). TC )value.

[0049] In one exemplary embodiment of this disclosure, thermal cycling parameters can be determined by curing a photosensitive resin composition containing polyimide resin to prepare a film sample with a thickness of 10 μm and measuring its physical properties.

[0050] In one exemplary embodiment of this disclosure, the membrane's I TC Alternatively, the thermal cycling index may refer to a value obtained by measuring the physical properties included in Equation 1 of a film sample prepared for evaluating a photosensitive resin composition, which is calculated using the measured physical properties.

[0051] By comparing cycle index values, photosensitive resin compositions exhibiting excellent elongation, sensitivity, and / or substrate adhesion can be provided, and can form highly reliable insulating films.

[0052] Specifically, it has thermal cycling parameters (I) within the desired range. TC The membrane can be evaluated as having high quality, and the photosensitive resin composition used to prepare the membrane can be evaluated as having high quality.

[0053] In one exemplary embodiment of this disclosure, the thermal cycling index (I TC The value can be 1000 or greater. Specifically, the thermal cycling index can be 1100 or greater, 1200 or greater, 1300 or greater, 1400 or greater, 1500 or greater, 1600 or greater, 1700 or greater, 1800 or greater, 1900 or greater, or 2000 or greater.

[0054] In one exemplary embodiment of this disclosure, the thermal cycling index (I TC The value can be 4000 or lower. Specifically, the thermal cycling index (I) TC The value can be 3900 or lower, 3800 or lower, 3700 or lower, 3600 or lower, 3500 or lower, 3400 or lower, 3300 or lower, 3200 or lower, 3100 or lower, or 3000 or lower.

[0055] In one exemplary embodiment of this disclosure, the thermal cycling index (I TC () can be a unitless value. Specifically, since it is a value calculated by substituting the measured value of a specific physical property according to Equation 1, it can be a unitless value.

[0056] The units for the physical properties are as follows: Y is the Young's modulus of the membrane (GPa), T is the tensile strength of the membrane (MPa), E is the elongation at break of the membrane (%), C is the coefficient of thermal expansion of the membrane (ppm / ℃), and C Cu is the coefficient of thermal expansion of copper (ppm / ℃).

[0057] In other words, the measured values ​​of the physical properties substituted into Equation 1 are as follows: Y is the Young's modulus of the membrane (GPa), T is the tensile strength of the membrane (MPa), E is the elongation at break of the membrane (%), C is the coefficient of thermal expansion of the membrane (ppm / ℃), and CCu The coefficient of thermal expansion of copper is given by (ppm / ℃).

[0058] In other words, the measured values ​​of physical properties substituted into Equation 1 can be dimensionless values ​​obtained from the measurements of physical properties. For example, the coefficient of thermal expansion of copper can be 17 ppm / ℃, and C in Equation 1... Cu It can be 17.

[0059] If the thermal cycling index (I) TC If the values ​​meet the above range, the photosensitive resin composition used to prepare the film sample can be evaluated as having good quality. Through this evaluation, a photosensitive resin composition can be provided that exhibits good elongation, sensitivity, and / or adhesion to the substrate and allows for the formation of a highly reliable insulating film.

[0060] In one exemplary embodiment of this disclosure, the membrane can be a membrane sample prepared for evaluating a photosensitive resin composition, which is prepared by coating a photosensitive resin composition containing polyimide resin onto a substrate to form a membrane and then curing the membrane. There are no particular limitations on the method of coating the resin composition containing polyimide resin onto the substrate. For example, screen printing, offset printing, flexographic printing, inkjet printing, etc., can be used.

[0061] In one exemplary embodiment of this disclosure, curing can be performed at temperatures of 160°C or higher and 240°C or lower. Specifically, curing can be performed at temperatures of 170°C or higher, 180°C or higher, 190°C or higher, or 200°C or higher, and at temperatures of 230°C or lower, 220°C or lower, 210°C or lower, or 200°C or lower. For example, curing can be performed at 200°C for a predetermined time, such as 1 hour, but is not limited thereto.

[0062] In one exemplary embodiment of this disclosure, curing may further include pre-curing, and pre-curing may be performed at temperatures of 90°C or higher and 120°C or lower. Specifically, pre-curing may be performed at temperatures of 95°C or higher, 100°C or higher, or 105°C or higher, and at temperatures of 115°C or lower, 110°C or lower, or 105°C or lower. For example, pre-curing may be performed at 105°C for a predetermined time, such as 120 seconds, but is not limited thereto. Pre-curing may be performed prior to curing to ensure processability.

[0063] In one exemplary embodiment of this disclosure, curing can be performed by irradiation with light of wavelengths from 250 nm to 450 nm. Specifically, curing can be performed by irradiation with light of wavelengths of 260 nm, 270 nm, 280 nm, 290 nm, or 300 nm, or by irradiation with light of wavelengths of 440 nm, 430 nm, 420 nm, 410 nm, 400 nm, or 300 nm. Furthermore, as described later, light sources such as mercury vapor arc, carbon arc, or Xe arc can be used for irradiation. For example, for negative photosensitive resin compositions, curing can be performed using 200 mJ / cm² light. 2 Up to 900 mJ / cm 2 The curing can be performed using an i-line stepper motor, but is not limited to this. On the other hand, in the case of a positive photosensitive resin composition, curing can be carried out by adjusting the above-mentioned temperature conditions without any light irradiation.

[0064] In one exemplary embodiment of this disclosure, the film thickness can be 9 μm or greater and 11 μm or less. Specifically, the film thickness can be 9 μm or greater and 10 μm or less, or 10 μm or greater and 11 μm or less, specifically 10 μm. In other words, the thickness of the film sample prepared for evaluating the photosensitive resin composition can be 10 ± 1 μm. The thickness of the film sample can be varied depending on the curing method and the measurement method. If it is increased or decreased by a certain amount, the measured physical properties of the polyimide film may also change by a certain amount.

[0065] In one exemplary embodiment of this disclosure, after preparing a sample with dimensions of 10 mm × 100 mm and a thickness of 10 μm for a film sample prepared for evaluating a photosensitive resin composition, the Young's modulus can be measured at room temperature and at a rate of 5 mm / min using a universal testing machine (UTM).

[0066] In one exemplary embodiment of this disclosure, after preparing a 10 mm × 100 mm sample with a thickness of 10 μm for a film sample prepared for evaluating a photosensitive resin composition, the tensile strength of the film can be measured at room temperature and at a rate of 5 mm / min using a universal testing machine (UTM).

[0067] In one exemplary embodiment of this disclosure, after preparing a 10 mm × 100 mm sample with a thickness of 10 μm for a film sample prepared for evaluating a photosensitive resin composition, the elongation at break of the film can be measured at room temperature and at a rate of 5 mm / min using a universal testing machine (UTM).

[0068] In one exemplary embodiment of this disclosure, the coefficient of thermal expansion (CTE) can be measured using a thermal expansion analyzer at temperatures of 50°C or higher and 100°C or lower. Specifically, for film samples prepared for evaluating photosensitive resin compositions, the CTE can be measured by monitoring changes in thermal expansion at a temperature range of 50°C or higher and 100°C or lower, with the tensile force of the film sample set to 0.01 N or greater and 0.1 N or less, or 0.01 N or greater and 0.05 N or less, and the sample being cooled at a heating rate of 1°C / min or higher and 15°C / min or lower, or 5°C / min or higher and 10°C / min or lower, using a TMA (Q400). However, this method is not limited to this.

[0069] [Photosensitive Resin Composition]

[0070] An exemplary embodiment of this disclosure provides a photosensitive resin composition comprising a polyimide resin, wherein, when the photosensitive resin composition is cured to prepare a film with a thickness of 10 μm and the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film are measured, I, as defined by Equation 1, TC The value is 1000 or greater.

[0071] In one exemplary embodiment of this disclosure, if the film prepared from the photosensitive resin composition has a thermal cycling index (I) within the above-mentioned range through measurement of physical properties and evaluation of evaluation factors... TC If so, the photosensitive resin composition can be evaluated as having good quality. A photosensitive resin composition evaluated as having good quality can have good elongation, sensitivity, and / or adhesion to the substrate, and can form a highly reliable insulating film.

[0072] In one exemplary embodiment of this disclosure, for a film sample prepared to evaluate a photosensitive resin composition, the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film can be measured. The film sample is a 10 μm thick film prepared by curing the photosensitive resin composition. The preparation of the film and the measurement of its coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break can be the same as described above regarding the film evaluation method, and the measured values ​​of the physical properties substituted into Equation 1 can be dimensionless.

[0073] The coefficient of thermal expansion of the membrane, measured over a temperature range of 50°C or higher and 100°C or lower, can be 30 ppm / °C or higher and 80 ppm / °C or lower. Specifically, the coefficient of thermal expansion of the membrane sample, measured using a thermal expansion analyzer when heated and cooled at temperatures of 50°C or higher and 100°C or lower, can be 32 ppm / °C or higher, 34 ppm / °C or higher, 36 ppm / °C or higher, 38 ppm / °C or higher, or 40 ppm / °C or higher, and 78 ppm / °C or lower, 76 ppm / °C or lower, 74 ppm / °C or lower, 72 ppm / °C or lower, or 70 ppm / °C or lower. The coefficient of thermal expansion can be determined in this way due to the polyimide resin contained in the membrane.

[0074] If the film has a coefficient of thermal expansion within the aforementioned range, the heat resistance of the insulating film containing the photosensitive resin composition can be improved by mitigating thermal deformation. Furthermore, it can prevent damage to the semiconductor device comprising it during heat treatment of the metal thin film formed on the substrate due to heat, and it can also prevent warping of the metal thin film formed on the substrate.

[0075] The Young's modulus of the membrane can be 2.2 GPa or higher and 4.0 GPa or lower. Specifically, the Young's modulus of the membrane can be 2.3 MPa or higher, 2.4 GPa or higher, 2.5 GPa or higher, 2.6 GPa or higher, 2.7 GPa or higher, 2.8 GPa or higher, 2.9 GPa or higher, or 3.0 GPa or higher, and 3.9 GPa or lower, 3.8 GPa or lower, 3.7 GPa or lower, 3.6 GPa or lower, or 3.5 GPa or lower. This Young's modulus can be achieved due to the polyimide resin contained in the membrane.

[0076] The tensile strength of the membrane can be 100 MPa or higher and 200 MPa or lower. Specifically, the tensile strength of the membrane can be 110 MPa or higher, 120 MPa or higher, 130 MPa or higher, 140 MPa or higher, or 150 MPa or higher, and 190 MPa or lower, 180 MPa or lower, 170 MPa or lower, 160 MPa or lower, or 150 MPa or lower. This tensile strength is achieved due to the polyimide resin contained in the membrane.

[0077] The elongation at break of the membrane can be 40% or higher and 100% or lower. Specifically, the elongation at break of the membrane can be 45% or higher, 50% or higher, or 55% or higher, and 95% or lower, 90% or lower, or 85% or lower. This elongation at break can be achieved due to the polyimide resin contained in the membrane.

[0078] If the Young's modulus, tensile strength, and elongation at break of the membrane are within the above ranges, the required physical properties of the insulating film containing the photosensitive resin composition can be achieved.

[0079] In one exemplary embodiment of this disclosure, the photosensitive resin composition may further comprise a photoinitiator. Specifically, the photoinitiator is a substance that initiates the crosslinking and / or curing reaction of the photosensitive resin upon exposure to light, and any common photoinitiator may be used without limitation. In terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, compounds selected from one or more of the following may be used: acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, bimidazole-based compounds, oxime compounds, and thioxanthone-based compounds.

[0080] Specific examples of compounds based on acetophenone may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylprop-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylprop-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)but-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]prop-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)but-1-one, etc.

[0081] Compounds based on benzophenone can include, for example, benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0082] Specific examples of triazine-based compounds may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0083] Specific examples of biimidazole-based compounds may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2'-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group, etc. Specifically, among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are used.

[0084] Specific examples of oxime compounds can include o-ethoxycarbonyl-α-oxime imino-1-phenylprop-1-one, etc. Representative commercially available products are BASF's OXE-01 and OXE-02.

[0085] Thioxanone-based compounds may include, for example, 2-isopropylthioxanone, 2,4-diethylthioxanone, 2,4-dichlorothioxanone, 1-chloro-4-propoxythioxanone, etc.

[0086] Specifically, according to one exemplary embodiment of this disclosure, an oxime ester-based photoradical initiator can be used as the photoinitiator. For example, OXE-01, OXE-03, OXE-04, SPI-03, SPI-07, I367, etc., can be used, but are not limited thereto.

[0087] An exemplary embodiment of the photosensitive resin composition according to this disclosure comprises a polyimide resin and may also comprise a photoacid generator.

[0088] 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-based photoacid generators, nitrobenzyl sulfonate-based photoacid generators, sulfone-based photoacid generators, dioxime-based photoacid generators, triazine-based photoacid generators, etc., can be used.

[0089] In one exemplary embodiment of this disclosure, the photoacid generator can be an ionic photoacid generator (e.g., sulfonium salt or iodine). Salts), sulfonyldiazomethane, compounds based on N-sulfonyloxyimide, compounds based on benzoin sulfonate, compounds based on pyrophenol trisulfonate, compounds based on nitrobenzyl sulfonate, compounds based on sulfone, compounds based on dioxime, and combinations thereof.

[0090] Sulfonium salts are salts of sulfonium cations and sulfonate groups (the anions of sulfonic acids). Sulfonium cations include triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, 4-methylphenyldiphenylsulfonium, tris(4-methylphenyl)sulfonium, 4-tert-butylphenyldiphenylsulfonium, tris(4-tert-butylphenyl)sulfonium, tris(4-tert-butoxyphenyl)sulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, (3,4-di-tert-butoxyphenyl)diphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethoxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethoxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, dimethyl-2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, diphenylmethylsulfonium, methyl-2-oxopropylphenylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, etc., as well as sulfonates including trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctanoate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanoic acidsulfonate, dodecylbenzenesulfonate, butyrate, methanesulfonate, etc.

[0091] iodine The salt is a salt of iodocation and sulfonate. Iodocations include diphenyliodo. bis(4-tert-butylphenyl)iodine 4-tert-butoxyphenyl iodine 4-Methoxyphenylphenyliodine wait.

[0092] Photoacid generators based on sulfonyl diazonium methane include bis(ethylsulfonyl)diazonium methane, such as bis(ethylsulfonyl)diazonium methane, bis(1-methylpropylsulfonyl)diazonium methane, bis(2-methylpropylsulfonyl)diazonium methane, bis(1,1-dimethylethylsulfonyl)diazonium methane, bis(cyclohexylsulfonyl)diazonium methane, bis(perfluoroisopropylsulfonyl)diazonium methane, bis(phenylsulfonyl)diazonium methane, bis(4-methylphenylsulfonyl)diazonium methane, and bis... (2,4-Dimethylphenylsulfonyl)diazomethane, bis(2-naphthylsulfonyl)diazomethane, etc.; sulfonyl carbonyl diazonethanes, such as 4-methylphenylsulfonylbenzoyl diazonethane, tert-butylcarbonyl-4-methylphenylsulfonyl diazonethane, 2-naphthylsulfonylbenzoyl diazonethane, 4-methylphenylsulfonyl-2-naphthyl diazonethane, methylsulfonylbenzoyl diazonethane, and tert-butoxycarbonyl-4-methylphenylsulfonyl diazonethane, etc.

[0093] Photoacid generators based on N-sulfonyloxyimides include succinimide, naphthalene dicarboxylic acid imide, phthalimide, cyclohexyl dicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, 7-oxabicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid imide, trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctyl sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octyl sulfonate, dodecylbenzenesulfonate, butyrate, methanesulfonate, etc.

[0094] Photoacid generators based on benzoin sulfonates include benzoin toluene sulfonate, benzoin methanesulfonate, and benzoin butyrate sulfonate, while photoacid generators based on nitrobenzyl sulfonate include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, and compounds in which the nitro group of the benzyl group is substituted with a trifluoromethyl group. Sulfone-based photoacid generators include bis(benzenesulfonyl)methane, bis(4-methylbenzenesulfonyl)methane, bis(2-naphthalenesulfonyl)methane, 2,2-bis(benzenesulfonyl)propane, 2,2-bis(4-methylbenzenesulfonyl)propane, 2,2-bis(2-naphthalenesulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)propanone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2,4-dimethyl-2-(p-toluenesulfonyl)pent-3-one, etc.

[0095] Photoacid generators based on oxime include bis-o-(p-toluenesulfonyl)-α-dimethyloxime, bis-o-(p-toluenesulfonyl)-α-dimethyloxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexyloxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione oxime, and bis-o-(p-toluenesulfonyl)-2-methyloxime. 3,4-Pentanedione glycoxime, bis-o-(n-butyryl)-α-dimethylglycoxime, bis-o-(n-butyryl)-α-dimethylglycoxime, bis-o-(n-butyryl)-α-dicyclohexylglycoxime, bis-o-(n-butyryl)-2,3-pentanedione glycoxime, bis-o-(n-butyryl)-2-methyl-3,4-pentanedione glycoxime Oxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butyryl)-α-dimethylglyoxime, bis-o-(perfluorooctyl)-α-dimethylglyoxime, bis-o-(cyclohexyl) bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

[0096] In one exemplary embodiment of this disclosure, the photosensitive resin composition may further comprise additives. Specifically, the additives may include one or more of surfactants, antioxidants, crosslinking agents, and solvents.

[0097] In one exemplary embodiment of this disclosure, the photosensitive resin composition may include all of the surfactant, antioxidant, crosslinking agent and solvent as additives.

[0098] 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.

[0099] In one exemplary embodiment of this disclosure, antioxidants can improve the elongation properties of the cured film or its adhesion to metallic materials after a reliability assessment. Furthermore, antioxidants can inhibit the oxidation of aliphatic groups or phenolic hydroxyl groups in 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.

[0100] In one exemplary embodiment of this disclosure, the crosslinking agent is not particularly limited, and any crosslinking agent 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 using the compounds exemplified above, a crosslinked structure can be formed during curing 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.

[0101] 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-Bi sOC-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 manufacturer. Two or more of these may also be used.

[0102] 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 HP-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 Dainippon Ink & 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 these.

[0103] 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.

[0104] 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.

[0105] 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; and other similar compounds. Diacrylates and dimethacrylates; 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.

[0106] Specifically, 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.

[0107] In one exemplary embodiment of this disclosure, the solvent can be any compound known in the art capable of forming a photosensitive resin composition, without particular limitation. As a non-limiting example, the solvent can be one or more compounds selected from esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0108] Ester-based solvents can 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.)), and 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, ethyl 3-ethylpropionic acid). Methyl oxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxypropionate (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.

[0109] Ether-based solvents can 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.

[0110] Ketone-based solvents can include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0111] Solvents based on aromatic hydrocarbons can include toluene, xylene, anisole, limonene, etc.

[0112] Solvents based on sulfoxides can include dimethyl sulfoxide, etc.

[0113] In one exemplary embodiment of this disclosure, the photosensitive resin composition may have a concentration of 350 mJ / cm². 2 Or lower sensitivity.

[0114] In one exemplary embodiment of this disclosure, the photosensitive resin composition may have a concentration of about 350 mJ / cm³. 2 Or lower, approximately 340 mJ / cm 2 Or lower, approximately 330 mJ / cm 2 Or lower, approximately 320 mJ / cm2 Or lower, or about 310 mJ / cm 2 Or even lower sensitivity. 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 assessed as having excellent physical properties as a sensitive material (e.g., easy formation of micropatterns).

[0115] In one exemplary embodiment of this disclosure, based on 100 parts by weight of polyimide resin, the photosensitive resin composition may contain 1 to 40 parts by weight of a photoinitiator, 5 to 50 parts by weight of a crosslinking agent, and 0.05 to 5 parts by weight of a surfactant.

[0116] 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.

[0117] If the photosensitive resin composition contains the above-mentioned components within the weight range of the above-mentioned parts by weight, then a smaller amount of photoacid generator can improve the sensitivity and physical properties and improve the adhesion to the substrate.

[0118] [Polyimide resin]

[0119] In one exemplary embodiment of this disclosure, the polyimide resin may be a polyimide resin having a structure represented by chemical formula 1 or a structure represented by chemical formula 2.

[0120] [Chemical Formula 1]

[0121]

[0122] [Chemical Formula 2]

[0123]

[0124] In chemical formula 1 and chemical formula 2,

[0125] For the portion that bonds with other substituents or repeating units,

[0126] L can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -SO2-, -CO-, or -OCO-.

[0127] R1 and R2 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups.

[0128] 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.

[0129] Ra and Rb may be the same or different, and independently represent hydrogen or structures represented by the chemical formula a.

[0130] [Chemical formula a]

[0131]

[0132] in

[0133] The portion that bonds to chemical formula 1 or chemical formula 2,

[0134] R3 is hydrogen or a substituted or unsubstituted alkyl group, and

[0135] q is an integer from 1 to 10.

[0136] Because the polyimide resin according to an exemplary embodiment of this disclosure comprises flexible chains, contains protecting groups that are insoluble in acids and bases, and is capable of melting at high temperatures, it advantageously exhibits improved elongation, hydrophilicity, and substrate adhesion. Photosensitive resin compositions comprising this polyimide resin exhibit easier micropatterning and better resolution when using a photoacid generator (PAG) compared to photosensitive resin compositions using a commonly used photoinitiator (PI), due to the smaller amount of photoacid generator used. Furthermore, the photosensitive resin compositions according to this disclosure can exhibit excellent sensitivity even when using small amounts of photoacid generator.

[0137] 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 substrate adhesion 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 prevented. Additionally, by lowering the glass transition temperature (Tg) of the polyimide resin… g This facilitates the diffusion of photoacid generators contained in negative photosensitive resin compositions, thereby improving resolution.

[0138] In this instruction manual, It can be a portion bonded to other substituents or repeating units, and can refer to a portion bonded to the main chain of the polymer of this disclosure.

[0139] In this specification, "polymer" refers to a compound composed of repeating units (basic units). A polymer can also refer to a material composed of macromolecules.

[0140] Examples of substituents are described below in this specification, but are not limited thereto.

[0141] In this specification, the term "substituted or unsubstituted" means substituted with one or more substituents 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 one or more of N, O, S or P atoms, or having no substituents at all.

[0142] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0143] 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.

[0144] 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.

[0145] In this specification, alkylene groups are the same as the alkyl groups mentioned above, except that the alkylene groups are divalent.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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, phenylenetriene It includes bases, fluorene groups, etc., but is not limited to these.

[0150] In this specification, arylene is the same as the aryl group described above, except that arylene is divalent.

[0151] In this specification, a heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom. It can have 2 to 30, particularly 2 to 20, carbon atoms, but there is no particular limitation on the number of carbon atoms. 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.

[0152] The above description of heterocyclic groups can be applied in this specification, except that heteroaryl groups are aromatic.

[0153] 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 may refer to a ring that is not an aromatic ring.

[0154] In one exemplary embodiment of this disclosure, L can be a direct bond, a substituted bond, or an unsubstituted bond. 1-30 Alkylene, substituted or unsubstituted C 6-30 aryl, -SO2-, -CO- or -OCO-.

[0155] In one exemplary embodiment of this disclosure, L can be a direct bond, a substituted bond, or an unsubstituted bond. 1-20 Alkylene, substituted or unsubstituted C 6-20 aryl, -SO2-, -CO- or -OCO-.

[0156] In one exemplary embodiment of this disclosure, L can be a direct bond, a substituted bond, or an unsubstituted bond. 1-10 Alkylene, substituted or unsubstituted C 6-12 aryl, -SO2-, -CO- or -OCO-.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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 chemical formula a.

[0161] [Chemical formula a]

[0162]

[0163] In one exemplary embodiment of this disclosure, chemical formula a can be one of the following structures, but is not limited thereto, and it is sufficient if q is an integer from 1 to 10.

[0164]

[0165] In one exemplary embodiment of this disclosure, R3 can be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0166] In one exemplary embodiment of this disclosure, R3 can be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0167] In one exemplary embodiment of this disclosure, R3 can be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0168] 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 more than 0 mol% and 100 mol% or less, based on the total content of the polyimide resin.

[0169] 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%.

[0170] In one exemplary embodiment of this disclosure, the content of the structure represented by chemical formula a based on the total content of the polyimide resin can be determined by commercially available NMR, and after the resin synthesis reaction is completed, the content (mol%) of the structure represented by chemical formula a can be determined by the number of protons in the aromatic ring of the polyimide in chemical formula a (the integral of the peaks at 6.41 ppm to 5.83 ppm (3H)) relative to the amount of OH before the reaction.

[0171] In one exemplary embodiment of this disclosure, chemical formula 1 or chemical formula 2 may be represented by one of the following structures.

[0172]

[0173] In the structural formula, Ra and Rb are the same as those defined in Chemical Formula 1 and Chemical Formula 2, and

[0174] It can be a portion that is bonded to other substituents or repeating units.

[0175] In one exemplary embodiment of this disclosure, the polyimide resin may also include a structure represented by the chemical formula E.

[0176] [Chemical Formula E]

[0177]

[0178] In chemical formula E,

[0179] For the portion that bonds with other substituents or repeating units,

[0180] Re1 is hydrogen or a substituted or unsubstituted alkyl group.

[0181] 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.

[0182] Re represents hydrogen or a structure represented by the chemical formula a.

[0183] In one exemplary embodiment of this disclosure, the structure represented by chemical formula E can be an end group of a polyimide resin.

[0184] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-30 alkyl.

[0185] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-20 alkyl.

[0186] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or substituted or unsubstituted C. 1-10 alkyl.

[0187] In one exemplary embodiment of this disclosure, Re1 can be hydrogen or a structure represented by chemical formula a.

[0188] 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.

[0189] In one exemplary embodiment of this disclosure, the polyimide resin may also comprise any of the structures represented by chemical formulas 3-1 to 3-4.

[0190] [Chemical Formula 3-1]

[0191]

[0192] [Chemical Formula 3-2]

[0193]

[0194] [Chemical Formula 3-3]

[0195]

[0196] [Chemical Formula 3-4]

[0197]

[0198] In chemical formulas 3-1 to 3-4

[0199] For the portion that bonds with other substituents or repeating units,

[0200] L1 to L3 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-,

[0201] L' and L'' may be the same or different, and are independently substituted or unsubstituted alkylene or substituted or unsubstituted arylene.

[0202] m is an integer from 1 to 5, where if m is 2 or greater, then L'' is the same or different.

[0203] Ra1 to Ra4 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups.

[0204] Ra1 to Ra4 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; and if Ra4 is 2 or greater, then Ra4 is identical or different.

[0205] Cy is a substituted or unsubstituted aliphatic or aromatic ring.

[0206] In one exemplary embodiment of this disclosure, one of chemical formulas 3-1 to 3-4 may be derived from the following chemical formulas.

[0207]

[0208]

[0209] 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 prepared insulating film may be easily damaged or have reduced adhesion. Furthermore, if the weight-average molecular weight of the polyimide resin exceeds 70,000 g / mol, the sensitivity may be reduced, and residues (e.g., scum) may remain on the insulating film.

[0210] [Insulating film]

[0211] An exemplary embodiment of this disclosure provides an insulating film comprising the above-described photosensitive resin composition or its cured product.

[0212] The insulating film may contain a photosensitive resin composition as is.

[0213] The insulating film may contain a cured product of a photosensitive resin composition.

[0214] The light source for curing the photosensitive resin composition according to an exemplary embodiment of this disclosure can be, for example, a mercury vapor arc, a carbon arc, an Xe arc, etc., that emits light with a wavelength of 250 nm to 450 nm, but is not limited thereto.

[0215] If necessary, the insulating film can be heated after the photosensitive resin composition has been cured.

[0216] Heating can be performed using heating devices such as hot plates, hot air circulators, infrared furnaces, etc., and can be carried out at 180°C to 250°C or 190°C to 220°C.

[0217] 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.

[0218] The insulating film may include a support or a substrate.

[0219] There are no particular 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 to these. Specifically, the support or substrate can be a silicon wafer.

[0220] There are no particular restrictions on the coating method, but methods such as spraying, roller coating, and spin coating can be used. Spin coating is generally widely used. Furthermore, after film formation, some residual solvent can be removed under reduced pressure.

[0221] 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 above range, 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).

[0222] In one exemplary embodiment of this disclosure, the insulating film comprising the photosensitive resin composition can have a yield of 99% or higher. The yield of the insulating film refers to the ratio of the number of insulating films evaluated as having good quality to the total number of insulating films prepared. Good quality can mean that when the insulating film undergoes a thermal cycling (TC) test subject to thermal shock, the insulating film exhibits an increase in resistance of less than 50% compared to before the TC test. In other words, the insulating film comprising the photosensitive resin composition can have a yield of 99% or higher as defined by Equation 2 after the TC test of the insulating film.

[0223] [Equation 2]

[0224] Yield (%) = (Np1 / Nt1) × 100

[0225] In equation 2,

[0226] Np1 represents the number of insulating films assessed as having good quality, and

[0227] Nt1 represents the total number of insulating films prepared.

[0228] Here, "insulating film" refers to an evaluation substrate formed on a substrate on which copper wiring is formed, and may also mean a substrate including an insulating film made of the same photosensitive resin composition as the "film sample" prepared for evaluating physical properties. Furthermore, apart from pattern formation, the conditions for forming the insulating film included in the evaluation substrate may be the same as the conditions for forming the aforementioned film sample.

[0229] For example, an "evaluation substrate" can refer to a substrate on which an insulating film pattern with a thickness of 5 μm to 10 μm has been formed by forming copper wiring on a silicon wafer, coating the copper wiring with a photosensitive resin composition, and then developing it after exposure and curing. After forming a flux coating and solder balls on the insulating film pattern, electrodes can be connected.

[0230] Here, TC testing can refer to thermal cycling (TC) testing, which involves applying thermal shock by repeating 700 cycles of 30 minutes each at low temperature (-55°C) and high temperature (125°C).

[0231] Since the insulating film according to an exemplary embodiment of the present disclosure comprises a photosensitive resin composition exhibiting high elongation, low sensitivity and excellent adhesion to the substrate, it can suppress wafer warpage within a semiconductor device using the insulating film and provide excellent reliability.

[0232] [Semiconductor Devices]

[0233] An exemplary embodiment of this disclosure provides a semiconductor device including the insulating film.

[0234] In addition to the insulating film, semiconductor devices may also include various components commonly used in the art.

[0235] In one exemplary embodiment of this disclosure, the semiconductor device including the insulating film can have a yield of 99% or higher. The yield of a semiconductor device refers to the ratio of the number of semiconductor devices evaluated as having good quality to the total number of semiconductor devices manufactured. "Good" can mean that when a semiconductor device undergoes a thermal cycling (TC) test subject to thermal shock, the semiconductor device exhibits an increase in resistance of less than 50% compared to before the TC test. In other words, the semiconductor device including the insulating film can have a yield of 99% or higher, as defined by Equation 3, after the TC test of the "semiconductor device".

[0236] [Equation 3]

[0237] Yield (%) = (Np2 / Nt2) × 100

[0238] In equation 3,

[0239] Np2 is the number of semiconductor devices evaluated as having good quality, and

[0240] Nt2 represents the total number of semiconductor devices fabricated.

[0241] "Semiconductor device" can refer to a semiconductor device comprising an insulating film pattern with copper wiring formed on a silicon wafer, and can also refer to a semiconductor device comprising an insulating film prepared from the same photosensitive resin composition as a "film sample" prepared for evaluating physical properties. Except for the patterning, the conditions for forming the insulating film included in the semiconductor device can be the same as the conditions for forming the film sample.

[0242] Furthermore, thermal cycling (TC) testing of semiconductor devices can be performed under the same conditions as TC testing of insulating films.

[0243] Since a semiconductor device according to an exemplary embodiment of this disclosure comprises a photosensitive resin composition exhibiting high elongation, low sensitivity and excellent adhesion to the substrate, warping of the wafer within the semiconductor device using the insulating film can be prevented, and excellent reliability can be provided.

[0244] The present disclosure is described in detail below by way of examples. However, embodiments of the present disclosure may be modified in several different forms, and the scope of the present disclosure should not be construed as limited to the embodiments described below. The embodiments provided in this specification are intended to describe the present disclosure more fully to those skilled in the art.

[0245] Invention Embodiments

[0246] Aggregate Examples

[0247] Aggregation Example 1

[0248] Under a nitrogen atmosphere, 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.25 equivalents of polyetheramine (D-400, Jeffamine), 1.35 equivalents of 4,4'-oxophthalic anhydride, and 0.16 equivalents of 3-aminophenol were dissolved in propylene glycol methyl ether acetate (PGMEA). Toluene was then added at 150 °C, and the reaction was carried out overnight at 180 °C using a Dean-Stark apparatus. After the reaction, toluene was removed from the Dean-Stark apparatus, and residual toluene was removed by multiple displacements of PGMEA. The residual monomers were identified by NMR, and polymer 1-1 was prepared by terminating the reaction. The molecular weight of polymer 1-1 was determined by gel permeation chromatography (GPC). The weight-average molecular weight was determined to be 17,000 g / mol.

[0249] <Polymer 1-1>

[0250]

[0251] In polymer 1-1, n, o, and p are values ​​that give the polymer a weight-average molecular weight of 17,000 g / mol. n is an integer from 2 to 15, o is an integer from 5 to 40, and p is an integer from 2 to 15.

[0252] Example 2 of Aggregation

[0253] Under a nitrogen atmosphere, 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.1 equivalents of 4,4'-oxophthalic anhydride, and 0.13 equivalents of 3-aminophenol were dissolved in PGMEA. Toluene was then added at 150 °C, and the reaction was carried out overnight at 180 °C using a Dean-Stark apparatus. After the reaction, toluene was removed from the Dean-Stark apparatus, and residual toluene was removed by multiple displacements of the PGMEA. The residual monomers were identified by NMR, and polymer 1-2 was prepared by terminating the reaction. The molecular weight of polymer 1-2 was determined by gel permeation chromatography (GPC). The weight-average molecular weight was determined to be 18,000 g / mol.

[0254] <Polymer 1-2>

[0255]

[0256] In polymers 1-2, o is a value that gives the polymer a weight-average molecular weight of 18,000 g / mol. o is an integer from 5 to 40.

[0257] Example 3 of Aggregation

[0258] Under a nitrogen atmosphere, 0.6 equivalents of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.4 equivalents of polyetheramine (ED-2003, Jeffamine), 1.1 equivalents of 4,4'-oxophthalic anhydride, and 0.13 equivalents of 3-aminophenol were dissolved in PGMEA. Toluene was then added at 150 °C, and the reaction was carried out overnight at 180 °C using a Dean-Stark apparatus. After the reaction, toluene was removed from the Dean-Stark apparatus, and residual toluene was removed by multiple displacements of the PGMEA. The residual monomers were identified by NMR, and polymers 1-3 were prepared by terminating the reaction. The molecular weight of polymers 1-3 was determined by gel permeation chromatography (GPC). The weight-average molecular weight was determined to be 23,000 g / mol.

[0259] <Polymers 1-3>

[0260]

[0261] Synthesis example

[0262] Synthesis example 1

[0263] After adding 0.1 equivalents of triethylamine (based on polyimide OH), 0.32 equivalents of 2-isocyanoethyl acrylate, and PGMEA to polymer 1-1 prepared in Polymer Example 1 and stirring at 80°C, the reaction was terminated after NMR analysis showed that 2-isocyanoethyl acrylate disappeared at 5.64 ppm (2H) and a new peak appeared at 3.15 ppm (2H). The total number of OH groups in the polymer was determined by NMR from the total area of ​​the aromatic rings, and the R corresponding to formula a (i.e., OH group) was determined using the average of the peaks at 6.41 (1H), 6.12 (1H), and 5.83 (1H). The proportion of hydrogen atoms substituted was determined. A total of 30 mol% was substituted. The weight-average molecular weight of the polymer, measured by gel permeation chromatography (GPC), was 21,000 g / mol. The structure of polymer 2-1 prepared in Synthesis Example 1 is as follows.

[0264] <Polymer 2-1>

[0265]

[0266] In polymer 2-1, n, o, and p are values ​​that give the polymer a weight-average molecular weight of 21,000 g / mol. n is an integer from 2 to 15, o is an integer from 5 to 40, and p is an integer from 2 to 15.

[0267] Synthesis example 2

[0268] Polymer 2-2 was synthesized in the same manner as in Synthesis Example 1, except that polymer 1-2 from Synthesis Example 2 was used instead of polymer 1. The R corresponding to chemical formula a (i.e., ...) was determined. The proportion of hydrogen substituted in polymer 2-2 was 30 mol%. The weight-average molecular weight of polymer 2-2 was determined to be 22,000 g / mol by gel permeation chromatography (GPC). The structure of polymer 2-2 prepared in Synthesis Example 2 is as follows.

[0269] <Polymer 2-2>

[0270]

[0271] In polymer 2-2, o is a value that gives the polymer a weight-average molecular weight of 22,000 g / mol. o is an integer from 5 to 40.

[0272] Synthesis example 3

[0273] Polymers 2-3 were synthesized in the same manner as in Synthesis Example 1, except that polymers 1-3 from Synthesis Example 3 were used instead of polymer 1. The R corresponding to chemical formula a (i.e., ...) was determined. The proportion of hydrogen substituted in polymer 2-3 was 30 mol%. The weight-average molecular weight of polymer 2-3 was determined to be 24,000 g / mol by gel permeation chromatography (GPC). The structure of polymer 2-3 prepared in Synthesis Example 3 is as follows.

[0274] <Polymer 2-3>

[0275]

[0276] Examples and Comparative Examples

[0277] Preparation Example 1 - Preparation of Photosensitive Resin Composition

[0278] The photosensitive resin composition was prepared using the components listed in Table 1. Specifically, the photosensitive resin composition was prepared based on 100 parts by weight of polyimide resin, using the components listed in Table 1 and 200 parts by weight of solvent (PGMEA).

[0279] [Table 1]

[0280]

[0281] In Table 1, B through E are as follows:

[0282] B: OXE-01 (BASF)

[0283] C: Polyethylene glycol (200) diacrylate (Miramer M282, Miwon)

[0284] D: Polyethylene glycol (200) diacrylate (Miramer M286, Miwon)

[0285] E: BYK-331 (BYK-Chemie)

[0286] Preparation Example 2: Membrane Preparation

[0287] The films of Preparation Examples 2-1 to 2-7, with a thickness of 10 μm, were prepared by curing the photosensitive resin compositions of Preparation Examples 1-1 to 1-7 under the following conditions. Specifically, the prepared photosensitive resin compositions were spin-coated onto a substrate. Subsequently, soft baking (SOB) was performed, followed by post-baking (PB) after exposure at an appropriate sensitivity. The film preparation conditions are as follows.

[0288] SOB 105℃ / 120 seconds, PB 200℃ / 1 hour, thickness 10 μm

[0289] Exposure: 200 mJ / cm 2 Up to 900 mJ / cm2 i-line stepper

[0290] Test Example - Measurement and Evaluation of Membrane Physical Properties

[0291] The physical properties of the membranes obtained in Preparation Examples 2-1 to 2-7 were measured by the following methods, and the results are shown in Table 2.

[0292] Test Example 1 - Coefficient of Thermal Expansion (CTE)

[0293] The membrane was prepared to a size of 5 mm × 20 mm, and the sample was mounted using an accessory. The thickness of the membrane sample was set to 10 μm, and the length was set to 16 mm. After a first heating process by setting the force on the stretched membrane sample to 0.01 N and heating the sample to a temperature of 50 °C or higher to 100 °C or lower at a heating rate of 10 °C / min, the change in thermal expansion during cooling at a rate of 10 °C / min from 100 °C or lower to 50 °C or higher was measured using a TMA (TA's Q400). The results are shown in Table 2.

[0294] Test Example 2 - Elongation at break, tensile strength and Young's modulus

[0295] After preparing membrane samples with dimensions of 10 mm × 100 mm and a thickness of 10 μm using the membranes prepared in Preparation Examples 2-1 to 2-7, the elongation at break (%), tensile strength (MPa), and Young's modulus (GPa) of each membrane sample were measured at room temperature using a universal testing machine (UTM) at a rate of 5 mm / min. The results are shown in Table 2.

[0296] Test Example 3 - Calculation of Thermal Cycling Parameters

[0297] The thermal cycling parameters (I) are calculated based on the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the membrane samples measured in Test Example 1 and Test Example 2, according to Equation 1. TC The evaluation results are presented in Table 2.

[0298] [Equation 1]

[0299]

[0300] (Y: Young's modulus of the membrane / (GPa), T: Tensile strength of the membrane / (MPa), E: Elongation at break of the membrane / (%), C: Coefficient of thermal expansion of the membrane / (ppm / ℃), C Cu Coefficient of thermal expansion of copper (ppm / ℃)

[0301] Test Example 4 - Reliability Assessment (TC Test)

[0302] Prepare the photosensitive resin compositions obtained from the above preparation examples 1-1 to 1-7.

[0303] After forming copper wiring on a silicon wafer, the photosensitive resin compositions of Preparation Examples 1-1 to 1-7 were each coated onto the copper wiring. Then, an insulating film pattern with a thickness of 10 μm was formed by exposure, curing, and development. Subsequently, a flux coating and solder balls were formed on the insulating film pattern, and an evaluation substrate containing the photosensitive resin compositions obtained in Preparation Examples 1-1 to 1-7 was prepared by connecting electrodes. The conditions for forming the insulating film pattern are as follows.

[0304] SOB 105℃ / 120 seconds, PB 200℃ / 1 hour, thickness 10 μm

[0305] Exposure: 200 mJ / cm 2 Up to 900 mJ / cm 2 i-line stepper

[0306] Development: 23°C, 2.38 wt% TMAH (tetramethylammonium hydroxide) solution, immersion, rinse with deionized water.

[0307] The reliability of the substrate (i.e., the insulating film containing the photosensitive resin composition) was evaluated by performing a thermal cycling (TC) test, which involves repeating 700 cycles of 30 minutes each at low temperature (-55°C) and high temperature (125°C).

[0308] Specifically, when the yield rate defined by Equation 2 is 99% or higher after TC testing, the insulating film is evaluated as having good quality.

[0309] [Equation 2]

[0310] Yield (%) = (Np1 / Nt1) × 100

[0311] In equation 2,

[0312] Np1 represents the number of insulating films assessed as having good quality, and

[0313] Nt1 represents the total number of insulating films prepared.

[0314] After TC testing, a yield rate of 99% or higher is indicated as "O", and a yield rate below 99% is indicated as "X".

[0315] [Table 2]

[0316]

[0317] Referring to Table 1, the films according to Examples 1 to 5 exhibit good heat resistance with thermal expansion measurement (C, CTE) values ​​of 60 ppm / °C or lower, as well as satisfactory physical properties required for insulating films used in semiconductor devices, such as elongation at break, tensile strength, Young's modulus, etc. They also show thermal cycling indexes (IT) of 1000 or higher after thermal cycling (TC) testing. TC A high yield and a positive thermal cycling index (I0.05) indicate excellent reliability of the insulating film. On the other hand, the thermal cycling index (I0.05) also demonstrates good performance. TC The insulating films prepared from Comparative Example 1 and Comparative Example 2, whose values ​​were below 1000, had poor reliability, with a yield rate of less than 99% after thermal cycling tests.

[0318] In other words, it was determined that the photosensitive resin compositions of Examples 1 to 5 according to this disclosure can form insulating films with good elongation, sensitivity, and / or adhesion to the substrate, and TC testing confirmed that the insulating films containing the photosensitive resin compositions also have excellent reliability. It can be seen that the photosensitive resin compositions according to an exemplary embodiment of this disclosure can form highly reliable insulating films in a simpler manner by measuring specific physical properties of the film samples and evaluating evaluation factors.

[0319] Furthermore, it can be seen that the insulating film and semiconductor device according to an exemplary embodiment of the present disclosure can have high reliability because they contain a photosensitive resin composition having high elongation, low sensitivity and excellent adhesion to the substrate, wherein warping of the wafer in the semiconductor device using the insulating film is prevented.

[0320] 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.

Claims

1. A photosensitive resin composition comprising polyimide resin, in, When the photosensitive resin composition is cured to prepare a film with a thickness of 10 μm and the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film are measured, I, as defined by Equation 1 TC Value 1000 or greater: [Equation 1] ， in I TC The thermal cycling index of the membrane. Y is the Young's modulus of the membrane. T is the tensile strength of the membrane. E is the elongation at break of the membrane. C is the coefficient of thermal expansion of the membrane, and C Cu is the coefficient of thermal expansion of copper.

2. The photosensitive resin composition according to claim 1, wherein the curing is performed at 160°C or higher and 240°C or lower.

3. The photosensitive resin composition according to claim 1, wherein the coefficient of thermal expansion is measured using a coefficient of thermal expansion analyzer at a temperature of 50°C or higher and 100°C or lower.

4. The photosensitive resin composition according to claim 1, wherein the polyimide resin is a polyimide resin comprising a structure represented by chemical formula 1 or a structure represented by chemical formula 2: [Chemical Formula 1] ， [Chemical Formula 2] ， In chemical formula 1 and chemical formula 2 For the portion that bonds with other substituents or repeating units, L can be a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -SO2-, -CO-, or -OCO-. R1 and R2 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. Ra and Rb may be the same or different, and independently represent hydrogen or structures represented by the chemical formula a. [Chemical formula a] ， In chemical formula a The portion that bonds to chemical formula 1 or chemical formula 2, R3 is hydrogen or a substituted or unsubstituted alkyl group, and q is an integer from 1 to 10.

5. The photosensitive resin composition according to claim 4, wherein the polyimide resin further comprises a structure represented by chemical formula E as an end group: [Chemical Formula E] ， In chemical formula E 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, and if re1 is 2 or greater, then two or more re1 values ​​are the same or different. Re represents hydrogen or a structure represented by the chemical formula a.

6. The photosensitive resin composition according to claim 4, wherein the polyimide resin is a polyimide resin further comprising any one of the structures represented by chemical formulas 3-1 to 3-4: [Chemical Formula 3-1] ， [Chemical Formula 3-2] ， [Chemical Formula 3-3] ， [Chemical Formula 3-4] ， In chemical formulas 3-1 to 3-4 For the portion that bonds with other substituents or repeating units, L1 to L3 may be the same or different, and are independently direct bonds, substituted or unsubstituted alkylene groups, substituted or unsubstituted aryl groups, -O-, -CO-, -S-, -COO-L'-OCO-, or -O-(L")mO-. 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 Ra4 may be the same or different, and are independently hydrogen or substituted or unsubstituted alkyl groups. Ra1 to Ra4 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; and if Ra4 is 2 or greater, then Ra4 is identical or different. Cy is a substituted or unsubstituted aliphatic or aromatic ring.

7. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises additives, wherein the additives further comprise one or more of surfactants, antioxidants, crosslinking agents and solvents.

8. An insulating film comprising a photosensitive resin composition or a cured product thereof according to any one of claims 1 to 7.

9. A semiconductor device comprising the insulating film according to claim 8.

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