WO2021171697A1 - 感光性樹脂組成物、感光性樹脂組成物の選別方法、パターン硬化膜の製造方法、及び半導体装置の製造方法 - Google Patents

感光性樹脂組成物、感光性樹脂組成物の選別方法、パターン硬化膜の製造方法、及び半導体装置の製造方法 Download PDF

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Publication number
WO2021171697A1
WO2021171697A1 PCT/JP2020/040109 JP2020040109W WO2021171697A1 WO 2021171697 A1 WO2021171697 A1 WO 2021171697A1 JP 2020040109 W JP2020040109 W JP 2020040109W WO 2021171697 A1 WO2021171697 A1 WO 2021171697A1
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Prior art keywords
photosensitive resin
resin composition
cured film
strip sample
film
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Ceased
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PCT/JP2020/040109
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English (en)
French (fr)
Japanese (ja)
Inventor
一行 満倉
裕貴 今津
優 青木
卓也 小峰
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Resonac Corp
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Showa Denko Materials Co Ltd
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Application filed by Showa Denko Materials Co Ltd filed Critical Showa Denko Materials Co Ltd
Priority to JP2022503085A priority Critical patent/JP7212832B2/ja
Priority to US17/801,378 priority patent/US12405198B2/en
Priority to CN202080097092.3A priority patent/CN115151868B/zh
Priority to KR1020227029840A priority patent/KR20220145837A/ko
Publication of WO2021171697A1 publication Critical patent/WO2021171697A1/ja
Anticipated expiration legal-status Critical
Priority to JP2023002247A priority patent/JP7764867B2/ja
Priority to JP2025086562A priority patent/JP2025113409A/ja
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/32—Investigating strength properties of solid materials by application of mechanical stress by applying repeated or pulsating forces
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/01—Manufacture or treatment
    • H10W20/071—Manufacture or treatment of dielectric parts thereof
    • H10W20/081—Manufacture or treatment of dielectric parts thereof by forming openings in the dielectric parts
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0001—Type of application of the stress
    • G01N2203/0005—Repeated or cyclic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0014—Type of force applied
    • G01N2203/0016—Tensile or compressive
    • G01N2203/0017—Tensile
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0058—Kind of property studied
    • G01N2203/006—Crack, flaws, fracture or rupture
    • G01N2203/0067—Fracture or rupture
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0058—Kind of property studied
    • G01N2203/0069—Fatigue, creep, strain-stress relations or elastic constants
    • G01N2203/0073—Fatigue
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/02—Details not specific for a particular testing method
    • G01N2203/022—Environment of the test
    • G01N2203/0222—Temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/02—Details not specific for a particular testing method
    • G01N2203/026—Specifications of the specimen
    • G01N2203/0298—Manufacturing or preparing specimens
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/20—Bump connectors, e.g. solder bumps or copper pillars; Dummy bumps; Thermal bumps
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/20—Bump connectors, e.g. solder bumps or copper pillars; Dummy bumps; Thermal bumps
    • H10W72/251—Materials
    • H10W72/252—Materials comprising solid metals or solid metalloids, e.g. PbSn, Ag or Cu
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/20—Bump connectors, e.g. solder bumps or copper pillars; Dummy bumps; Thermal bumps
    • H10W72/29—Bond pads specially adapted therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/90—Bond pads, in general

Definitions

  • the present invention relates to a photosensitive resin composition, a method for selecting a photosensitive resin composition, a method for producing a pattern cured film, and a method for producing a semiconductor device.
  • semiconductor packages In order to realize high-speed transmission and miniaturization of semiconductor devices, semiconductor packages have been proposed in which materials having different physical characteristics are combined in a complicated manner to increase the density. In such a semiconductor package, the stress on the semiconductor element and the rewiring layer becomes large, so that a material having high mechanical reliability while relaxing the stress is required.
  • a stress-relaxable surface protective film is required, and the fan-out type package has layers that can withstand higher stress than before.
  • An insulating film is required.
  • the materials used for the surface protective film and the interlayer insulating film are required to be thermoset at a temperature of 250 ° C. or lower.
  • a pattern cured film formed from a polyimide resin, a polybenzoxazole resin, or a photosensitive resin composition containing a phenol resin, which can be cured at a low temperature is used as a surface protective film or an interlayer insulating film.
  • Japanese Unexamined Patent Publication No. 2008-309858 Japanese Unexamined Patent Publication No. 2007-57595 Japanese Unexamined Patent Publication No. 2008-076583 International Publication No. 2010/073948 Japanese Unexamined Patent Publication No. 2018-185480
  • the photosensitive resin composition for forming the surface protective film or the interlayer insulating film has high reliability even when cured at a temperature of 250 ° C. or lower in order to reduce stress, warpage, and damage to the semiconductor element.
  • Materials are required, and there is a strong demand for photosensitive materials that can be developed with an alkaline aqueous solution due to environmental load, safety, and device surface restrictions. However, it is difficult for these materials to satisfy sufficient mechanical reliability in a package form with high stress, and cracks may occur in the protective film or the insulating film.
  • the present disclosure is photosensitive, which can be developed with an alkaline aqueous solution, does not generate cracks even when cured at 250 ° C. or lower, and forms a cured film having high mechanical and thermal shock reliability.
  • Provided are a simple method for sorting a resin composition, a photosensitive resin composition sorted by this sorting method, a method for manufacturing a pattern cured film using the photosensitive resin composition sorted by this sorting method, and a method for manufacturing a semiconductor device. The purpose is to do.
  • One aspect of the present disclosure is that the resin film of the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 and heat-treated under nitrogen at 150 to 250 ° C. for 1 to 3 hours to obtain a film thickness of 10 ⁇ m and a width of 10 ⁇ m.
  • a strip sample of a 10 mm cured film was prepared, and a fatigue test was conducted in which the strip sample was repeatedly pulled under the conditions that the set temperature was 25 ° C, the distance between chucks was 20 mm, the test speed was 5 mm / min, and the stress of repeated load was 100 MPa.
  • the present invention relates to a method for selecting a photosensitive resin composition, which selects a photosensitive resin composition in which the number of times of pulling until the strip sample breaks in a fatigue test is 100 cycles or more.
  • the fatigue test of the strip sample may be performed under the conditions that the set temperature is ⁇ 55 ° C., the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of repeated load is 120 MPa.
  • the resin film of the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 and heat-treated under nitrogen at 150 to 250 ° C. for 1 to 3 hours to obtain a film thickness of 10 ⁇ m.
  • a strip sample of a cured film with a width of 10 mm was prepared, and the set temperature was 25 ° C, the distance between chucks was 20 mm, the test speed was 5 mm / min, the stress of repeated load was 100 MPa, or the set temperature was -55 ° C, between chucks.
  • the number of pulls until the strip sample breaks is 100 cycles or more.
  • Another aspect of the present disclosure is a step of applying and drying the photosensitive resin composition selected by the above-mentioned method for selecting a photosensitive resin composition on a part or the entire surface of a substrate to form a resin film, and the resin.
  • the present invention relates to a method for producing a pattern cured film, which comprises a step of exposing at least a part of the film, a step of developing the exposed resin film to form a pattern resin film, and a step of heating the pattern resin film.
  • Another aspect of the present disclosure relates to a method for manufacturing a semiconductor device, which comprises a pattern-cured film formed by the above-mentioned method for manufacturing a pattern-cured film as an interlayer insulating layer or a surface protective layer.
  • the present disclosure provides a method for selecting a photosensitive resin composition that does not cause cracks due to thermal shock such as a temperature cycle test when the photosensitive resin composition is used as a surface protective film or an interlayer insulating film.
  • the materials are sorted by a fatigue test at 25 ° C or -55 ° C, a low temperature not seen in the past.
  • Fatigue fracture resistance at 25 ° C and -55 ° C correlates with thermal shock reliability (package reliability), and thermal shock reliability (sample preparation and evaluation takes time) by a simple and ready-to-evaluate fatigue test.
  • Package reliability can be evaluated easily in a short time.
  • the present invention is not limited to the following embodiments.
  • the term "process” is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.
  • the term "layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the amount of each component in the composition in the present specification when a plurality of substances corresponding to each component are present in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total amount of.
  • (meth) acrylic acid means at least one of "acrylic acid” and its corresponding "methacrylic acid”. The same applies to other similar expressions such as (meth) acrylate.
  • the resin film of the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 and exposed to nitrogen at 150 to 250 ° C. for 1 to 3 hours.
  • the set temperature is 25 ° C
  • the distance between chucks is 20 mm
  • the test speed is 5 mm / min
  • the stress of repeated load is 100 MPa.
  • a fatigue test in which the strip sample is repeatedly pulled is performed, and a photosensitive resin composition in which the number of pulls until the strip sample breaks in the fatigue test is 100 cycles or more is selected.
  • the resin film of the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 and exposed to nitrogen at 150 to 250 ° C., 1 to 3 After heat treatment for a period of time, a strip sample of a cured film having a thickness of 10 ⁇ m and a width of 10 mm was prepared. Under these conditions, a fatigue test in which the strip sample is repeatedly pulled is performed, and a photosensitive resin composition in which the number of pulls until the strip sample breaks in the fatigue test is 100 cycles or more is selected.
  • the photosensitive resin composition is applied onto a substrate and dried to form a resin film.
  • the type of the base material is not particularly limited, and for example, a silicon wafer having copper formed on its surface can be used.
  • the photosensitive resin composition may be applied onto the copper surface of the silicon wafer using a spin coater.
  • a resin pattern is formed on copper. Exposure condition of the resin film, 500 ⁇ 1500mJ / cm 2, or a 800 ⁇ 1200mJ / cm 2.
  • a resin pattern can be obtained by developing the exposed resin film with a developing solution such as an alkaline aqueous solution.
  • the resin pattern can be heated under nitrogen to form a cured film of the resin pattern.
  • the heating temperature of the resin pattern may be 160 to 230 ° C. or 180 to 220 ° C., and the heating time may be 1.5 to 2.5 hours or 1.8 to 2.2 hours.
  • a fatigue test of a strip sample is performed, and a photosensitive resin composition in which the number of times of pulling until the strip sample breaks is 100 cycles or more is selected.
  • the fatigue test can be performed under any of the following conditions (1) or (2).
  • Condition (1) The strip sample is repeatedly pulled (0 to 100 MPa) under the conditions that the set temperature is 25 ° C., the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeating load is 100 MPa.
  • Condition (2) The strip sample is repeatedly pulled (0 to 120 MPa) under the conditions that the set temperature is ⁇ 55 ° C., the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of repeated load is 120 MPa.
  • a photosensitive resin composition in which the number of times of pulling until the strip sample breaks in the fatigue test is 100 cycles or more, a cured film having excellent thermal shock reliability characteristics can be obtained, and a temperature cycle test of a semiconductor package can be obtained. It is possible to reduce the occurrence of cracks and the like.
  • the number of times a strip sample breaks in a fatigue test is defined as "fatigue fracture resistance".
  • the number of pulls when the strip sample is broken is preferably 250 cycles or more, more preferably 500 cycles or more, further preferably 800 cycles or more, and particularly preferably 1000 cycles or more.
  • the photosensitive resin composition selected by the method for selecting the photosensitive resin composition according to the present embodiment a package having a large difference in linear expansion coefficient between copper and resin, stress derived from an organic material such as a sealing material, and a large warp. Even in this case, cracks in the resin layer can be suppressed, and even in a package form having high stress, it is possible to manufacture a semiconductor device having excellent reliability against thermal shock due to a temperature cycle.
  • the breaking elongation rate of the strip sample in the tensile test in which the strip sample after 100 cycles of the fatigue test is pulled under the conditions of a set temperature of 25 ° C., a distance between chucks of 20 mm, and a test speed of 5 mm / min is 10 to 60%. Is preferable.
  • the elongation rate of the cured film is 10% or more, it becomes easy to relax the stress, and the stress tends to concentrate on the semiconductor element or other organic member to improve the reliability of the semiconductor package.
  • the elongation rate of the cured film is 60% or less, the cured film tends to be less likely to become fragile during the temperature cycle.
  • the elongation rate of the cured film is more preferably 15% or more in terms of being able to further relax stress, and further preferably 20% or more in terms of improving crack resistance.
  • the temperature of the sample After 100 cycles of the fatigue test of condition (1) or condition (2) using an autograph (AG-1kNXplus) with a special constant temperature bath manufactured by Shimadzu Corporation. It is obtained by pulling under the conditions of ⁇ 55 ° C., a distance between chucks of 20 mm, and a test speed of 5 mm / min, and measuring the elongation rate at break.
  • the yield stress of the strip sample (cured film of the photosensitive resin composition) measured in the tensile test is preferably 120 to 200 MPa.
  • the yield stress is 120 MPa or more, the cured film is less likely to be plastically deformed in a package having a high stress, and problems are less likely to occur due to repeated stress.
  • the yield stress of the cured film is 200 MPa or less, the impact resistance tends to be improved.
  • the yield stress of the cured film is more preferably 125 MPa or more, and further preferably 140 MPa or more, in that crack resistance after thermal history can be maintained.
  • the yield stress is the curve obtained by plotting the horizontal axis with the elongation rate and the vertical axis with the stress in the above tensile test, the tangent line in the plot showing the elongation rate of 5% and the tangent line in the plot showing the elongation rate of 15%. It is obtained by setting the value of the stress at the intersection with and as the yield stress.
  • the stress value at 1000 cycles can be obtained as the critical stress of the cured film of the photosensitive resin composition.
  • the critical stress of the cured film is preferably 120 MPa or more, and more preferably 125 MPa or more in that crack resistance after thermal history can be maintained.
  • the Young's modulus of the strip sample measured in the above tensile test is preferably 0.5 to 2.8 GPa.
  • the Young's modulus of the cured film is 0.5 GPa or more, the cured film is less likely to be deformed when stress is applied, and it becomes easy to suppress the concentration of stress on the material having a high Young's modulus mounted on the semiconductor package.
  • the Young's modulus of the cured film is 2.8 GPa or less, the stress is relaxed by the cured film and it becomes difficult to damage the semiconductor element.
  • the Young's modulus of the cured film is more preferably 1.0 to 2.7 GPa, and even more preferably 1.4 to 2.6 GPa.
  • Young's modulus can be calculated from the slope in the elongation range of 0 to 5% by plotting the horizontal axis with the elongation rate and the vertical axis with the stress in the above tensile test.
  • the glass transition temperature (Tg) of the cured film of the photosensitive resin composition according to the present embodiment is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 180 ° C. or higher. ..
  • Tg of the cured film is 150 ° C. or higher, the stress at the time of temperature change such as a temperature cycle test can be reduced.
  • the upper limit of Tg of the cured film may be 300 ° C. or lower.
  • Tg uses a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd. to measure the viscoelasticity of the strip sample in a temperature range of 40 to 260 ° C. with a chuck distance of 20 mm, a frequency of 10 Hz, and a temperature rise rate of 5 ° C./min. Then, the temperature showing the maximum value of tan ⁇ can be obtained as the glass transition temperature.
  • the coefficient of linear expansion of the cured film of the photosensitive resin composition according to the present embodiment is preferably 20 to 100 ppm / ° C. (20 ⁇ 10-6 to 100 ⁇ 10-6 / ° C.).
  • the coefficient of linear expansion of the cured film is 100 ppm / ° C. or less, stress at the time of temperature change can be suppressed.
  • the coefficient of linear expansion of the cured film is 20 ppm / ° C. or higher, it becomes easy to suppress the occurrence of cracks.
  • the adhesion ratio of the cured film of the photosensitive resin composition according to the present embodiment to the electroplated copper substrate is preferably 75% or more.
  • the adhesion rate is 75% or more, the cured film is peeled off from the underlying electroplated copper pattern when stress is applied, and the stress is concentrated on the material having a high adhesion rate to the electroplated copper mounted on the semiconductor package.
  • Tend. The higher the adhesion rate, the better, more preferably 90% or more, further preferably 95% or more, and particularly preferably 100%.
  • the adhesion rate can be measured by the following procedure. First, the photosensitive resin composition is applied to an electroplated copper substrate using a spin coater so that the film thickness after curing is 10 ⁇ m, and heated under nitrogen at 200 ° C. for 2 hours to form a cured film. do. Next, a temperature cycle test was repeated 200 times on the cured membrane under the conditions of an atmospheric pressure air atmosphere, a temperature of -65 to 150 ° C., and a stop time of 15 minutes, in which -65 ° C. was changed as the start temperature and the end temperature. After that, the cured film is cut in a grid pattern by the cross-cut method specified in JIS K 5600-5-6. A tape peeling test of the cured film cut in a grid pattern is performed, and the ratio (adhesion rate) of the lattice (cured film) adhering to the electroplated copper substrate is calculated.
  • the photosensitive resin composition according to the embodiment has 100 or more cycles of pulling until the strip sample breaks when the above-mentioned fatigue test is performed.
  • the photosensitive resin composition may be a positive type photosensitive resin composition or a negative type photosensitive resin composition.
  • the photosensitive resin composition can include, for example, (A) an alkali-soluble resin, (B) a thermosetting resin, and (C) a photosensitive agent.
  • A an alkali-soluble resin
  • B a thermosetting resin
  • C a photosensitive agent
  • the photosensitive resin composition according to the present embodiment may contain an alkali-soluble resin as the component (A) from the viewpoint of improving the alkali developability.
  • the alkali-soluble resin means a resin that is soluble in an aqueous alkaline solution (developing solution).
  • the alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • a TMAH aqueous solution having a concentration of 2.38% by mass is used for development. It can be confirmed, for example, that the component (A) is soluble in an alkaline developer as follows.
  • a varnish obtained by dissolving a resin in an arbitrary solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having a film thickness of about 5 ⁇ m.
  • a substrate such as a silicon wafer
  • This is immersed in any of an aqueous solution of TMAH, an aqueous solution of metal hydroxide or an aqueous solution of organic amine at 20 to 25 ° C.
  • the coating film can be uniformly dissolved, the resin can be considered soluble in the alkaline developer.
  • the component (A) is not particularly limited as long as it dissolves in a 2.38 mass% TMAH aqueous solution, but is preferably a compound having a phenolic hydroxyl group or a carboxyl group.
  • Examples of the compound having a phenolic hydroxyl group include a polyimide resin, a polybenzoxazole resin, a polyamide resin, a novolac resin which is a condensate of phenol-formaldehyde, a cresol and formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.
  • Examples thereof include polyhydroxystyrene or a copolymer thereof, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin, and an acrylic polymer having a phenolic hydroxyl group.
  • the acrylic polymer having a phenolic hydroxyl group is not particularly limited, but an acrylic polymer represented by the following general formula (1) can be used.
  • R 1 represents a hydrogen atom or a methyl group.
  • the phenolic hydroxyl group equivalent of the acrylic polymer having a phenolic hydroxyl group is preferably 200 to 700 g / eq from the viewpoint of pattern forming property and reduction of voids during thermal pressure bonding.
  • An acrylic polymer having a phenolic hydroxyl group is a copolymer having a structural unit represented by the formula (1) and a structural unit other than the structural unit represented by the formula (1) (hereinafter, simply referred to as "another structural unit").
  • the other structural unit which may be, is a structural unit derived from a monomer copolymerizable with a monomer having a structural unit represented by the formula (1).
  • the monomer having another structural unit is not particularly limited, but a (meth) acrylate compound or a vinyl compound can be used.
  • Examples of monomers having other structural units include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxyethoxyethyl acrylate, and acrylic acid.
  • the component (A) may contain a compound having a carboxyl group.
  • the compound having a carboxyl group is not particularly limited, but an acrylic polymer having a carboxyl group in the side chain is preferably used.
  • an alkali-soluble resin having a Tg of 150 ° C. or higher (A1) and an alkali-soluble resin having a Tg of 120 ° C. or lower may be mixed and used. With such a configuration, a cured film having more excellent reliability can be obtained.
  • the Tg of the component (A) was obtained by using a viscoelastic analyzer (trade name "RSA-2", manufactured by Leometrics Co., Ltd.) for a film of the component (A) at a temperature rise rate of 5 ° C./min and a frequency of 1 Hz. , The peak temperature of tan ⁇ when measured under the condition of measurement temperature ⁇ 150 to 300 ° C.
  • RSA-2 viscoelastic analyzer
  • the weight average molecular weight (Mw) of the component (A) is preferably controlled in the range of 2000 to 200,000, more preferably 3000 to 100,000, and further preferably 5000 to 80,000.
  • the Mw of the alkali-soluble resin (A1) is preferably 2000 to 50,000, more preferably 4000 to 30000 from the viewpoint of reliability, and 2000 to 30000 from the viewpoint of resolution at the time of pattern formation. Is more preferable.
  • the Mw of the alkali-soluble resin (A2) is preferably 10,000 to 100,000, more preferably 15,000 to 100,000 from the viewpoint of reliability, and 15,000 to 70,000 from the viewpoint of resolution at the time of pattern formation. Is more preferable.
  • Mw is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the measuring device for example, high performance liquid chromatography (trade name "CR4A", manufactured by Shimadzu Corporation) can be used.
  • the component (A) may contain an alkali-soluble resin having an imide group from the viewpoint of further improving fatigue fracture resistance.
  • an acrylic polymer obtained by polymerizing a (meth) acrylate compound having an imide group is preferably used because the concentration of the imide group can be arbitrarily adjusted.
  • alkali-soluble resin having an imide group alkali-soluble polyimide can also be used. From the viewpoint of resolution, the alkali-soluble resin having an imide group is preferably used in combination with a novolak resin or a phenol resin.
  • the alkali-soluble resin having an imide group may be a copolymer of a (meth) acrylate compound having an imide group and a (meth) acrylate compound having a phenolic hydroxyl group or a carboxyl group.
  • examples of the (meth) acrylate compound having an imide group include N-acryloyloxyethyl hexahydrophthalimide and N-methacryloyloxyethyl hexahydrophthalimide.
  • the ratio of the structural units based on the (meth) acrylate compound having an imide group is 10% by mass or more in that the toughness of the cured film can be improved based on all the monomer units constituting the alkali-soluble resin having an imide group. It is preferable that it is 20% by mass or more in that it can sufficiently impart fatigue fracture resistance, and it is preferably 60% by mass or less in that it does not impair alkali solubility.
  • the content of the alkali-soluble resin having an imide group is preferably 10% by mass or more in that the toughness of the cured film can be improved based on the total amount of the component (A), and deterioration can be suppressed during thermal history. It is more preferably 20% by mass or more, and further preferably 30% by mass or more in that fatigue fracture resistance can be sufficiently imparted.
  • the component (A) may include an alkali-soluble resin having an imide group and an alkali-soluble resin having no imide group.
  • the content of the alkali-soluble resin having an imide group is preferably 5% by mass or more in that the strength of the cured film can be improved based on the total amount of solids contained in the photosensitive resin composition, and the fatigue fracture strength. It is more preferable that it is 10% by mass or more in that it can improve, and it is even more preferable that it is 20% by mass or more in that it can maintain sufficient fatigue fracture strength even after thermal deterioration of the cured film, and the toughness of the cured film is improved. It is more preferably 30% by mass or more in terms of being able to be formed, and more preferably 80% by mass or less in terms of maintaining fine processability during development of the photosensitive resin composition.
  • the alkali-soluble resin having an imide group contained in the photosensitive resin composition is particularly preferably 30 to 80% by mass.
  • thermosetting resin The photosensitive resin composition according to the present embodiment preferably contains (B) a thermosetting resin.
  • thermosetting resin include acrylate resin, epoxy resin, cyanate ester resin, maleimide resin, allylnadiimide resin, phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, and diallylphthalate resin.
  • thermosetting resins include thermosetting resins.
  • the thermosetting resin is a compound having any one selected from a methylol group, an alkoxyalkyl group, and a glycidyl group. Is more preferable.
  • a compound having a glycidyl group as a component (B) in a photosensitive resin composition, when the resin film after pattern formation is heated and cured, it reacts with the component (A) to form a bridging structure. .. This makes it possible to prevent brittleness and melting of the cured film.
  • the compound having a glycidyl group conventionally known compounds can be used. Examples of the compound having a glycidyl group include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin, and polyalkylene glycol di. Glycidyl ether can be mentioned.
  • the amount of the compound having a glycidyl group to be blended in the photosensitive resin composition is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of solubility in an alkaline aqueous solution and physical properties of the cured film. More preferably, 3 to 25 parts by mass.
  • the photosensitive resin composition according to the present embodiment preferably contains (C) a photosensitive agent.
  • a photoradical polymerization initiator that generates radicals by light irradiation or a photoacid generator that generates acid by light irradiation can be used.
  • photoradical polymerization initiator examples include an alkylphenone-based photopolymerization initiator, an acylphosphine-based photopolymerization initiator, an intramolecular hydrogen abstraction type photopolymerization initiator, and a cationic photopolymerization initiator.
  • These photopolymerization initiators are Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369, Omnirad 369, Omnirad, EG It can be purchased as an Initiator OXE01, an Infracure OXE02, an Infracure OXE03, an Initiator OXE04, etc. manufactured by the company.
  • These photoradical polymerization initiators may be used alone or in combination of two or more, depending on the purpose, application and the like.
  • the photoacid generator has a function of generating an acid by light irradiation and increasing the solubility of the light-irradiated part in an alkaline aqueous solution.
  • the photoacid generator include an o-quinone diazode compound, an aryldiazonium salt, a diallyliodonium salt, and a triarylsulfonium salt.
  • the o-quinone diazide compound is preferable because of its high sensitivity.
  • o-quinone diazide compound for example, a compound obtained by condensing an o-quinone diazidosulfonyl chloride with a hydroxy compound, an amino compound or the like in the presence of a dehydrochloric acid agent can be used.
  • the reaction temperature may be 0-40 ° C. and the reaction time may be 1-10 hours.
  • o-quinone diazide sulfonyl chloride examples include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Can be mentioned.
  • hydroxy compound examples include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- ⁇ 1- (4-hydroxyphenyl).
  • amino compound examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide.
  • O-aminophenol O-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-) Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Examples thereof include 3-amino-4-hydroxyphenyl) hexafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.
  • 1,1-bis (4-hydroxyphenyl) -1- [4- ⁇ 1- (4-Hydroxyphenyl) -1-methylethyl ⁇ phenyl] A compound obtained by condensing ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride, tris (4-hydroxyphenyl) methane or It is preferable to use a compound obtained by condensing tris (4-hydroxyphenyl) ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride.
  • Examples of the dehydrochloric acid agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.
  • Examples of the reaction solvent include dioxane, acetone, methyl ethyl ketone, tetrahydrofun, diethyl ether, and N-methylpyrrolidone.
  • the o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound are prepared so that the total number of moles of the hydroxy group and the amino group is 0.5 to 1 mol with respect to 1 mol of o-quinonediazide sulfonyl chloride. It is preferable to blend.
  • the preferred blending ratio of the dehydrochloric acid agent and o-quinonediazidosulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 molar equivalents.
  • the content of the component (C) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity, and 5 to 50 parts.
  • mass is more preferred, and 5 to 30 parts by mass is even more preferred.
  • the photosensitive resin composition according to the embodiment can contain a small molecule compound having a phenolic hydroxyl group.
  • the small molecule compound having a phenolic hydroxyl group is used to increase the dissolution rate of the exposed portion when developing with an alkaline aqueous solution and to improve the sensitivity.
  • the component (D) reacts with the component (A) to form a bridging structure. This makes it possible to prevent brittleness and melting of the cured film.
  • the molecular weight of the component (D) is preferably 2000 or less, and the number average molecular weight (Mn) is preferably 94 to 2000 in consideration of the solubility in an alkaline aqueous solution and the balance between the photosensitive characteristics and the physical characteristics of the cured film, 108. It is more preferably ⁇ 2000, and even more preferably 108-1500.
  • the small molecule compound having a phenolic hydroxyl group As the small molecule compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the compound represented by the following general formula (2) has an effect of promoting dissolution of the exposed portion and melting at the time of curing of the resin film. It has an excellent balance of preventive effects and is particularly preferable.
  • X represents a single bond or a divalent organic group
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom or a monovalent organic group, respectively
  • s and t represent a hydrogen atom or a monovalent organic group, respectively.
  • u and v independently indicate an integer of 0 to 4, respectively.
  • the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative.
  • the divalent organic group represented by X include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. Allylene groups having 6 to 30 carbon atoms, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced with halogen atoms such as fluorine atoms, sulfon groups, carbonyl groups, ether bonds, thioether bonds, and amides. Bonding can be mentioned. Among these, a divalent organic group represented by the following general formula (3) is preferable.
  • X' is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), and one of those hydrogen atoms.
  • a group in which a part or all is substituted with a halogen atom, a sulfone group, a carbonyl group, an oxy group, a thio group, or an amide group is indicated, R "indicates a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group, and g is 1 to 1. It represents an integer of 10 and the plurality of R's may be the same or different from each other.
  • the blending amount of the low molecular weight compound having a phenolic hydroxyl group is 1 to 50 with respect to 100 parts by mass of the component (A) from the viewpoints of the development time, the allowable range of the unexposed portion residual film ratio, and the characteristics of the cured film. It is preferably parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 25 parts by mass.
  • the photosensitive resin composition according to the embodiment contains components such as a compound that produces an acid by heating, an elastomer, a dissolution accelerator, a dissolution inhibitor, a coupling agent, a solvent, a surfactant, and a leveling agent. It may be further contained.
  • the photosensitive resin composition according to the embodiment can contain a compound that produces an acid by heating.
  • a compound that produces an acid by heating it becomes possible to generate an acid when the patterned resin film is heated, and the reaction between the component (A), the component (B), and the component (D), that is, The thermal cross-linking reaction is promoted, and the heat resistance of the pattern cured film is improved.
  • the compound that produces an acid by heating also generates an acid by light irradiation, the solubility of the exposed portion in the alkaline aqueous solution is increased. Therefore, the difference in solubility between the unexposed portion and the exposed portion in the alkaline aqueous solution becomes larger, and the resolution is further improved.
  • the compound that produces an acid by heating is preferably one that produces an acid by heating to, for example, 50 to 250 ° C.
  • Examples of the compound that produces an acid by heating include a salt formed from a strong acid such as an onium salt and a base, and an imide sulfonate.
  • Examples of the onium salt include diaryliodonium salts such as aryldiazonium salt and diphenyliodonium salt; di (alkylaryl) iodonium salt such as diaryliodonium salt and di (t-butylphenyl) iodonium salt; and trialkyl such as trimethylsulfonium salt.
  • Examples thereof include a sulfonium salt; a dialkyl monoaryl sulfonium salt such as a dimethylphenyl sulfonium salt; a diaryl monoalkyl iodonium salt such as a diphenyl methyl sulfonium salt; and a triaryl sulfonium salt.
  • di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid
  • the salt formed from the strong acid and the base in addition to the above-mentioned onium salt, the following salt formed from the strong acid and the base, for example, a pyridinium salt can also be used.
  • the strong acid include aryl sulfonic acids such as p-toluene sulfonic acid and benzene sulfonic acid; perfluoroalkyl sulfonic acids such as camphor sulfonic acid, trifluoromethane sulfonic acid and nonafluorobutane sulfonic acid; and methane sulfonic acid and ethane sulfonic acid.
  • alkyl sulfonic acids such as acids and butane sulfonic acids.
  • examples of the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.
  • imide sulfonate examples include naphthoylimide sulfonate and phthalimide sulfonate.
  • R 5 is, for example, a cyano group
  • R 6 is, for example, a methoxyphenyl group, a phenyl group, etc.
  • R 7 is, for example, an aryl such as a p-methylphenyl group, a phenyl group, etc. It is an alkyl group such as a group, a methyl group, an ethyl group or an isopropyl group, or a perfluoroalkyl group such as a trifluoromethyl group or a nonafluorobutyl group.
  • R 8 is, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a methylphenyl group or a phenyl group, a perfluoroalkyl group such as a trifluoromethyl group or a nonafluorobutyl group.
  • Examples of the group bonded to the N atom of the sulfonamide structure represented by the general formula (5) include 2,2'-bis (4-hydroxyphenyl) hexafluoropropane and 2,2'-bis (4-hydroxy). Examples include phenyl) propane and di (4-hydroxyphenyl) ether.
  • the blending amount is 0.1 to 30 parts by mass, 0.2 to 20 parts by mass, or 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). May be.
  • the photosensitive resin composition according to the embodiment may contain an elastomer component in addition to the above. Elastomers are used to impart flexibility to the cured product of the photosensitive resin composition.
  • the elastomer conventionally known elastomers can be used, but it is preferable that the Tg of the polymer constituting the elastomer is 20 ° C. or lower.
  • elastomer examples include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These can be used alone or in combination of two or more.
  • the blending amount may be 1 to 50 parts by mass or 5 to 30 parts by mass with respect to 100 parts by mass of the component (A).
  • the blending amount of the elastomer is 1 part by mass or more, the heat impact resistance of the cured film tends to be improved, and when it is 50 parts by mass or less, the resolution and the heat resistance of the obtained cured film are unlikely to decrease.
  • the compatibility and dispersibility with other components tend to be difficult to decrease.
  • dissolution accelerator By blending the dissolution accelerator into the photosensitive resin composition, the dissolution rate of the exposed portion when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved.
  • the dissolution accelerator conventionally known ones can be used.
  • the dissolution accelerator include compounds having a carboxy group, a sulfonic acid, or a sulfonamide group.
  • the blending amount can be determined by the dissolution rate in an alkaline aqueous solution, and can be, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A).
  • the dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the residual film thickness, development time, and contrast.
  • the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodine.
  • the blending amount is 0.01 to 20 parts by mass, 0.01 to 15 parts by mass, or 0 with respect to 100 parts by mass of the component (A) from the viewpoint of sensitivity and allowable range of development time. It may be 0.05 to 10 parts by mass.
  • the adhesiveness of the formed pattern cured film to the substrate can be enhanced.
  • the coupling agent include an organic silane compound and an aluminum chelate compound.
  • organic silane compound examples include vinyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, and n-.
  • the blending amount may be 0.1 to 20 parts by mass or 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • the coatability can be further improved.
  • a surfactant or leveling agent By blending a surfactant or a leveling agent into the photosensitive resin composition, the coatability can be further improved. Specifically, for example, by containing a surfactant or a leveling agent, striation (unevenness of film thickness) can be further prevented and developability can be further improved.
  • the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.
  • surfactants or leveling agents include, for example, Megafuck F171, F173, R-08 (trade name manufactured by DIC Corporation), Florard FC430, FC431 (trade name manufactured by Sumitomo 3M Ltd.), and organosiloxane polymer. Examples thereof include KP341, KBM303, KBM403, and KBM803 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name).
  • the blending amount may be 0.001 to 5 parts by mass or 0.01 to 3 parts by mass with respect to 100 parts by mass of the component (A).
  • the photosensitive resin composition has an effect that it can be easily applied to a substrate and a coating film having a uniform thickness can be formed by containing a solvent for dissolving or dispersing each component.
  • solvent examples include ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, and N.
  • N-dimethylformamide N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylenesulfone, diethylketone, diisobutylketone, methylamylketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether.
  • the solvent one type can be used alone or two or more types can be used in combination.
  • the blending amount of the solvent is not particularly limited, but it is preferable to adjust the proportion of the solvent in the photosensitive resin composition to be 20 to 90% by mass.
  • the photosensitive resin composition according to the present embodiment uses an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). Can be developed.
  • an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the method for producing a pattern cured film (resist pattern) is a step of applying and drying the above-mentioned photosensitive resin composition on a part or the entire surface of a substrate to form a resin film (coating / drying (deposition)). Step), a step of exposing at least a part of the resin film (exposure step), a step of developing the exposed resin film to form a pattern resin film (development step), and a patterned pattern resin film (step). It includes a step (heat treatment step) of heating the photosensitive resin film).
  • exposure step exposing at least a part of the resin film
  • development step a step of developing the exposed resin film to form a pattern resin film
  • a patterned pattern resin film step
  • each step will be described.
  • the photosensitive resin composition according to the present embodiment is applied onto a substrate and dried to form a resin film.
  • the photosensitive resin composition is rotationally coated and coated on a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO 2 , SiO 2, etc.), silicon nitride, etc. using a spinner or the like.
  • a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO 2 , SiO 2, etc.), silicon nitride, etc. using a spinner or the like.
  • the substrate on which this coating film is formed is dried using a hot plate, an oven, or the like.
  • the drying temperature and drying time are not particularly limited, but may be 80 to 140 ° C. for 1 to 7 minutes. As a result, a photosensitive resin film is formed on the substrate.
  • the resin film formed on the substrate is irradiated with active rays such as ultraviolet rays, visible rays, and radiation through a mask.
  • active rays such as ultraviolet rays, visible rays, and radiation through a mask.
  • i-ray irradiation can be preferably used.
  • post-exposure heating PEB
  • the post-exposure heating temperature is preferably 70 to 140 ° C., and the post-exposure heating time is preferably 1 to 5 minutes.
  • the developing step the exposed portion of the resin film after the exposure step is removed with a developing solution, so that the resin film is patterned and a patterned resin film is obtained.
  • a developing solution for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH) is preferably used.
  • the base concentration of these aqueous solutions may be 0.1 to 10% by mass. Alcohols or surfactants may be added to the developer for use.
  • each of these may be blended in the range of 0.01 to 10 parts by mass or 0.1 to 5 parts by mass with respect to 100 parts by mass of the developing solution.
  • the developing solution is arranged on a resin film by a method such as shower development, spray development, immersion development, paddle development, etc., and 30 to 360 ° C. under the conditions of 18 to 40 ° C. Leave for a second. After being left to stand, the pattern resin film is washed by washing with water and performing spin drying.
  • the pattern cured film (resist pattern) can be formed by heat-treating the pattern resin film.
  • the heating temperature in the heat treatment step may be 250 ° C. or lower, 225 ° C. or lower, or 140 to 200 ° C. from the viewpoint of sufficiently preventing heat damage to the electronic device.
  • the heat treatment can be performed using, for example, an oven such as a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, or a microwave curing furnace. Further, either in the atmosphere or in an inert atmosphere such as nitrogen can be selected, but it is desirable under nitrogen because the oxidation of the pattern can be prevented. Since the above-mentioned heating temperature range is lower than the conventional heating temperature, damage to the substrate and the electronic device can be suppressed to a small extent. Therefore, by using the method for producing a pattern cured film according to the present embodiment, the electronic device can be produced with a high yield. It also leads to energy saving of the process. Further, according to the photosensitive resin composition according to the present embodiment, since the volume shrinkage (curing shrinkage) in the heat treatment step seen in the photosensitive polyimide or the like is small, it is possible to prevent a decrease in dimensional accuracy.
  • an oven such as a quartz tube furnace,
  • the heat treatment time in the heat treatment step may be a time sufficient for the photosensitive resin composition to cure, but it is preferably about 5 hours or less in consideration of work efficiency.
  • the heat treatment can be performed using a microwave curing device or a frequency variable microwave curing device in addition to the above-mentioned oven. By using these devices, it is possible to effectively heat only the resin film while keeping the temperature of the substrate and the electronic device at a desired temperature (for example, 200 ° C. or lower).
  • the microwave is irradiated in a pulse shape while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly.
  • the substrate contains metal wiring as in the case of electronic components described later
  • irradiating microwaves in a pulse shape while changing the frequency can prevent the generation of discharge from the metal and destroy the electronic components. Can be protected.
  • the physical characteristics of the cured film are less likely to deteriorate even if the curing temperature is lowered as compared with the case of using an oven (J. Photopolym. Sci. Technol., 18, 327-332 (2005). )reference).
  • the frequency of the variable frequency microwave is in the range of 0.5 to 20 GHz, but practically it may be in the range of 1 to 10 GHz or 2 to 9 GHz. Further, although it is desirable to continuously change the frequency of the microwave to be irradiated, in reality, the frequency is changed in a stepwise manner for irradiation. At that time, if the time for irradiating a single frequency microwave is as short as possible, standing waves, discharges from metals, etc. are unlikely to occur. Therefore, the irradiation time for microwaves is preferably 1 millisecond or less, preferably 100 microseconds or less. Is more preferable.
  • the output of the microwave to be irradiated varies depending on the size of the device or the amount of the object to be heated, but is generally in the range of 10 to 2000 W, and practically 100 to 1000 W, 100 to 700 W, or 100 to 500 W. good.
  • the output is 10 W or more, it becomes easy to heat the object to be heated in a short time, and when it is 2000 W or less, a rapid temperature rise is unlikely to occur.
  • the microwave it is preferable to irradiate the microwave by turning it on / off in a pulse shape.
  • the set heating temperature can be maintained, and damage to the cured film and the base material can be avoided, which is preferable.
  • the time for irradiating the pulsed microwave at one time varies depending on the conditions, but is preferably about 10 seconds or less.
  • a pattern cured film having good heat resistance can be obtained with sufficiently high sensitivity and resolution.
  • the pattern cured film according to this embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor element.
  • FIG. 1 to 5 are schematic cross-sectional views showing an embodiment of a manufacturing process of a semiconductor device having a multilayer wiring structure.
  • the structure 100 shown in FIG. 1 is prepared.
  • the structure 100 is formed on a semiconductor substrate 1 such as a Si substrate having a circuit element, a protective film 2 such as a silicon oxide film having a predetermined pattern on which the circuit element is exposed and covering the semiconductor substrate 1, and an exposed circuit element.
  • a semiconductor substrate 1 such as a Si substrate having a circuit element
  • a protective film 2 such as a silicon oxide film having a predetermined pattern on which the circuit element is exposed and covering the semiconductor substrate 1, and an exposed circuit element.
  • a first conductor layer 3 formed in the above, and an interlayer insulating layer 4 made of a polyimide resin or the like formed on the protective film 2 and the first conductor layer 3 by a spin coating method or the like are provided.
  • the structure 200 shown in FIG. 2 is obtained by forming the photosensitive resin layer 5 having the window portion 6A on the interlayer insulating layer 4.
  • the photosensitive resin layer 5 is formed by applying, for example, a photosensitive resin such as a rubber chloride type, a phenol novolac type, a polyhydroxystyrene type, or a polyacrylic acid ester type by a spin coating method.
  • the window portion 6A is formed by a known photographic etching technique so that the interlayer insulating layer 4 of a predetermined portion is exposed.
  • the photosensitive resin layer 5 is removed to obtain the structure 300 shown in FIG.
  • a dry etching means using a gas such as oxygen or carbon tetrafluoride can be used for etching the interlayer insulating layer 4.
  • the photosensitive resin layer 5 is removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window portion 6B.
  • the second conductor layer 7 is formed in the portion corresponding to the window portion 6B to obtain the structure 400 shown in FIG.
  • a known photographic etching technique can be used to form the second conductor layer 7.
  • the second conductor layer 7 and the first conductor layer 3 are electrically connected.
  • the surface protective layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7, and the semiconductor device 500 shown in FIG. 5 is obtained.
  • the surface protective layer 8 is formed as follows. First, the photosensitive resin composition according to the above-described embodiment is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by a spin coating method, and dried to form a resin film. Next, after irradiating a predetermined portion with light through a mask on which a pattern corresponding to the window portion 6C is drawn, the resin film is patterned by developing with an alkaline aqueous solution. Then, the resin film is cured by heating to form a film as the surface protective layer 8.
  • the surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, ⁇ rays, and the like, and the obtained semiconductor device 500 is excellent in reliability.
  • a method for manufacturing a semiconductor device having a two-layer wiring structure is shown, but when forming a three-layer or more multi-layer wiring structure, the above steps are repeated to form each layer. Can be done. That is, it is possible to form a multi-layer pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. Further, in the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed by using the photosensitive resin composition according to the present embodiment.
  • the electronic component according to the present embodiment has a pattern cured film formed by the above-mentioned manufacturing method as an interlayer insulating layer or a surface protective layer.
  • Electronic components include semiconductor devices, multilayer wiring boards, various electronic devices, and the like.
  • the pattern cured film can be used as a surface protective layer of a semiconductor device, an interlayer insulating layer, an interlayer insulating layer of a multilayer wiring board, and the like.
  • the electronic component according to the present embodiment is not particularly limited except that it has a surface protective layer or an interlayer insulating layer film formed by using the above-mentioned photosensitive resin composition, and can have various structures.
  • the above-mentioned photosensitive resin composition is excellent in stress relaxation property, adhesiveness, etc., it can also be used as various structural materials in packages having various structures developed in recent years. 6 and 7 show a cross-sectional structure of an example of such a semiconductor device.
  • FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of a semiconductor device.
  • the semiconductor device 600 shown in FIG. 6 has an Al having a pattern including a silicon chip 23, an interlayer insulating layer 11 provided on one surface side of the silicon chip 23, and a pad portion 15 formed on the interlayer insulating layer 11.
  • the wiring layer 12, the insulating layer 13 (for example, P—SiN layer) and the surface protective layer 14 which are sequentially laminated on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and the surface protective layer.
  • the island-shaped core 18 arranged in the vicinity of the opening on the 14 is in contact with the pad portion 15 in the opening of the insulating layer 13 and the surface protection layer 14, and is in contact with the surface of the core 18 opposite to the surface protection layer 14.
  • the semiconductor device 600 includes a cover coat layer 19 formed by covering the surface protection layer 14, the core 18, and the rewiring layer 16 and having an opening formed in a portion of the rewiring layer 16 on the core 18, and a cover coat.
  • a conductive ball 17 connected to the rewiring layer 16 with a barrier metal 20 sandwiched between the openings of the layer 19, a collar 21 for holding the conductive ball, and a cover coat layer 19 around the conductive ball 17 are provided.
  • the underfill 22 is provided.
  • the conductive ball 17 is used as an external connection terminal and is formed of solder, gold, or the like.
  • the underfill 22 is provided to relieve stress when mounting the semiconductor device 600.
  • FIG. 7 is a schematic cross-sectional view showing a wiring structure as an embodiment of a semiconductor device.
  • an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and an insulating layer 13 is formed on the pad portion 15 of the Al wiring layer.
  • the surface protective layer 14 is formed.
  • a rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to the upper part of the connecting portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 via the barrier metal 20.
  • the above-mentioned photosensitive resin composition forms not only the interlayer insulating layer 11 and the surface protective layer 14, but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. Can be used as a material for.
  • the cured product using the above-mentioned photosensitive resin composition has excellent adhesiveness to metal layers such as the Al wiring layer 12 and the rewiring layer 16, and a sealing material, and has a high stress relaxation effect.
  • the semiconductor device used for the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used for flip chips, etc. is extremely reliable.
  • the photosensitive resin composition according to the present embodiment is particularly preferably used for the surface protective layer 14 and / or the cover coat layer 19 of the semiconductor device having the rewiring layer 16 in FIGS. 6 and 7.
  • the film thickness of the surface protective layer or the cover coat layer may be, for example, 3 to 20 ⁇ m or 5 to 15 ⁇ m.
  • the photosensitive resin composition according to the present embodiment it is possible to cure using low temperature heating of 200 ° C. or lower in the above heat treatment step which conventionally required 300 ° C. or higher. Further, since the photosensitive resin composition according to the present embodiment has a small volume shrinkage (curing shrinkage) in the heat treatment step seen in the photosensitive polyimide or the like, it is possible to prevent a decrease in dimensional accuracy. Since the pattern cured film formed from the photosensitive resin composition according to the present embodiment has a high glass transition temperature, it becomes a surface protective layer having excellent heat resistance. As a result, electronic components such as semiconductor devices having excellent reliability can be obtained with good yield and high yield.
  • component (A) As the component (A), P-1 to P-9 were prepared. Table 1 summarizes Mw and Tg of P-1 to P-9.
  • Hexafluoropropane (trade name "BIS-AP-AF", manufactured by Central Glass Co., Ltd.) 14.64 g (0.04 mol), polyoxypropylene diamine (trade name “D-400", manufactured by BASF) 19.48 g ( 0.045 mol), 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl) bispropylamine (trade name "BY16-871EG", manufactured by Toray Dow Corning Co., Ltd.) 2.485 g (0.01 mol) and 80 g of N-methyl-2-pyrrolidone (NMP) as a solvent were charged, and the mixture was stirred to dissolve the amine component in the solvent.
  • NMP N-methyl-2-pyrrolidone
  • thermosetting resin (B-1): 4,4', 4''-Echiridentris [2,6- (methoxymethyl) phenol] (trade name "HMOM-TPHAP”, manufactured by Honshu Chemical Industry Co., Ltd.)
  • B-2) Bisphenol A bis (triethylene glycol glycidyl ether) ether (trade name "BEO-60E”, manufactured by Shin Nihon Rika Co., Ltd.)
  • D-1 1,1-bis (4-hydroxyphenyl) -1- [4- ⁇ 1- (4-hydroxyphenyl) -1-methylethyl ⁇ phenyl] ethane (trade name "TrsP-PA-MF”) , Made by Honshu Chemical Industry Co., Ltd.)
  • a photosensitive resin composition is applied to a 6-inch silicon wafer on which copper is formed by sputtering so that the film thickness after curing is 10 ⁇ m with a spin coater, and heated on a hot plate at 100 ° C. for 5 minutes.
  • To form a resin film 1000 mJ / cm 2 using a high-precision parallel exposure machine (trade name "EXM-1172-B- ⁇ ", manufactured by ORC Manufacturing Co., Ltd.) through a photomask designed to obtain a strip pattern with a width of 10 mm.
  • the resin film was exposed under the conditions and developed with a 2.38 mass% TMAH aqueous solution to obtain a strip pattern of the resin film.
  • the strip pattern was heated under nitrogen at 200 ° C. for 2 hours and then immersed in a copper etching solution to prepare a strip sample of a cured film having a thickness of 10 ⁇ m and a width of 10 mm.
  • the fatigue test of the strip sample was carried out under the following conditions using an autograph (AG-1kNXplus) with a special constant temperature bath manufactured by Shimadzu Corporation.
  • Condition (1) The strip sample is repeatedly pulled (0 to 100 MPa) under the conditions that the set temperature is 25 ° C., the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeating load is 100 MPa.
  • Condition (2) The strip sample is repeatedly pulled (0 to 120 MPa) under the conditions that the set temperature is ⁇ 55 ° C., the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of repeated load is 120 MPa.
  • yield stress In the above tensile test, the stress at the intersection of the tangent line in the plot showing the elongation rate of 5% and the tangent line in the plot showing the elongation rate of 15% obtained by plotting the horizontal axis with the elongation rate and the vertical axis with the stress. The value of was taken as the yield stress.
  • Young's modulus was calculated from the slope of the curve obtained by plotting the horizontal axis with the elongation rate and the vertical axis with the stress in the elongation range of 0 to 5%.
  • the strip sample prepared in the comparative example broke in less than 100 cycles of the fatigue test, the elongation, yield stress, and Young's modulus of the comparative example were measured using the strip sample not subjected to the fatigue test.
  • Glass-transition temperature Using a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd., the viscoelasticity of the strip sample was measured in a temperature range of 40 to 260 ° C. at a chuck distance of 20 mm, a frequency of 10 Hz, and a temperature rise rate of 5 ° C./min.
  • the temperature showing the maximum value of tan ⁇ was defined as the glass transition temperature (Tg).
  • Adhesion rate A photosensitive resin composition was applied to the surface of the electroplated copper substrate with a spin coater so that the film thickness after curing was 10 ⁇ m, and heated on a hot plate at 120 ° C. for 3 minutes to form a resin film. Next, the resin film was cured by heating in a nitrogen atmosphere at 200 ° C. for 2 hours to prepare a sample for evaluating the adhesion rate.
  • a temperature cycle test was repeated 200 times for the sample for evaluation of the adhesion rate under the conditions of atmospheric pressure air atmosphere, temperature -65 to 150 ° C., and stop time 15 minutes, and changing -65 ° C. as the start temperature and end temperature. After that, it was cut in a grid pattern by the cross-cut method specified in JIS K 5600-5-6. Next, a tape having an adhesion strength of 10 ⁇ 1N per 25 mm width is attached to a 25-mass lattice (cured film), and the tape is pulled vertically within 0.5 minutes within 5 minutes after adhesion. I peeled it off.
  • the number of lattices in which the cured film was peeled off along the edge of the cut or the lattices in which the cured film was peeled off at the intersection was measured, and the ratio (adhesion rate) of the lattices (cured film) adhering to the electroplated copper substrate was calculated.
  • the adhesion rate was evaluated as "A” when the adhesion rate was 100%, "B” when it was 75% or more and less than 100%, and "C” when it was less than 75%.
  • a photosensitive resin composition is applied to a 400 ⁇ m-thick 8-inch silicon wafer with a spin coater so that the film thickness after curing is 10 ⁇ m, heated at 100 ° C. for 5 minutes on a hot plate, and then 200 under nitrogen.
  • a first-layer cured film was prepared by heating at ° C. for 2 hours.
  • a seed layer was formed by a sputtering apparatus so that Cu was formed at 200 nm on Ti at 50 nm, a resist material was formed into a pattern, and electrolytic plating was performed so that the copper thickness was 5 ⁇ m.
  • the resist material was peeled off by NMP, and Cu and Ti were removed by etching to prepare a first layer copper pattern having a diameter of 350 ⁇ m.
  • a photomask designed to have a residual copper ratio of 70% by a copper mesh pattern was used.
  • a photosensitive resin composition was applied with a spin coater so that the cured film thickness on copper was 5 ⁇ m, and after heating on a hot plate at 100 ° C. for 5 minutes, a first layer copper pattern having a diameter of 350 ⁇ m was obtained.
  • a second layer of cured film was prepared by heating under nitrogen at 200 ° C. for 2 hours.
  • the resist material was patterned through a mask and electroplated so that the copper thickness was 5 ⁇ m.
  • the resist material was peeled off by NMP, and Cu and Ti were removed by etching to prepare a second layer copper pattern having a diameter of 240 ⁇ m.
  • a photomask designed so that the copper mesh pattern had a residual copper ratio of 30% was used.
  • Flux is applied on the second layer copper pattern with a diameter of 240 ⁇ m, and a solder ball with a diameter of 250 ⁇ m (Eco Solder Ball SM705 manufactured by Senju Metal Industry Co., Ltd.) is mounted. Under a nitrogen atmosphere, JEDEC (Semiconductor Technology Association; J- After reflowing under the profile conditions according to STD-020D), flux cleaning was performed to obtain a package for reliability evaluation.
  • JEDEC semiconductor Technology Association
  • the temperature cycle test of the above package was carried out under the condition that the JESD22-A104 condition B standard, which is a cycle of 15 minutes at -55 ° C and 15 minutes at 125 ° C, was repeated 1000 times, and the side wall of the second layer copper pattern having a diameter of 240 ⁇ m was 300. The location was observed.
  • Package reliability (“A” when the cracks are less than 5%, “B” when the cracks are 5 to 20%, and "C” when the cracks are more than 20%. Thermal shock reliability) was evaluated.
  • the fatigue tests under conditions (1) and (2) correlate with package reliability, and thermal shock requires time for sample preparation and evaluation by evaluating the fatigue fracture resistance of the cured film. It can be confirmed that the reliability (package reliability) can be easily evaluated in a short time. If a photosensitive resin composition having a fatigue fracture resistance of 100 cycles or more selected in a fatigue test is used, a pattern cured film having excellent thermal shock reliability (package reliability) can be formed, and a semiconductor device using this can also heat. Excellent impact reliability.

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