Photosensitive resin composition, sorting method of photosensitive resin composition, method for manufacturing patterned film, and method for manufacturing semiconductor device

Abstract

The present disclosure relates to a sorting method of a photosensitive resin composition, wherein a long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition, and performing a heat treatment at 150 to 250°C for 1 to 3 hours under nitrogen, and a fatigue test of repeatedly stretching the long strip sample is performed under a condition (1) in which a set temperature is 25°C, a distance between chucks is 20 mm, a test speed is 5 mm / min, and a stress of a repeated load is 100 MPa, or a condition (2) in which the set temperature is -55°C, the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 120 MPa, and the photosensitive resin composition in which the number of stretching until the long strip sample is broken in the fatigue test is 100 cycles or more is sorted. 2 A long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition, and performing a heat treatment at 150 to 250°C for 1 to 3 hours under nitrogen, and a fatigue test of repeatedly stretching the long strip sample is performed under a condition (1) in which a set temperature is 25°C, a distance between chucks is 20 mm, a test speed is 5 mm / min, and a stress of a repeated load is 100 MPa, or a condition (2) in which the set temperature is -55°C, the distance between chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 120 MPa, and the photosensitive resin composition in which the number of stretching until the long strip sample is broken in the fatigue test is 100 cycles or more is sorted.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition, a sorting method of the photosensitive resin composition, a manufacturing method of a pattern cured film, and a manufacturing method of a semiconductor device. BACKGROUND

[0002] In order to realize high speed transmission and miniaturization of semiconductor devices, semiconductor packages in which materials having different properties are complexly combined and highly densified have been proposed. In such semiconductor packages, stress to semiconductor elements and rewiring layers becomes large, and thus materials having high mechanical reliability while relieving stress are required.

[0003] In order to reduce stress to Low-k materials formed in semiconductor elements, surface protective films capable of relieving stress are required, and interlayer insulating films capable of withstanding higher stress than in the past are required in fan-out packages. Furthermore, in order to reduce low heat resistance of semiconductor elements and stress of semiconductor packages, materials used for surface protective films and interlayer insulating films are required to be heat cured at a temperature of 250°C or lower.

[0004] In response to such a requirement, pattern cured films formed of photosensitive resin compositions containing polyimide resins, polybenzoxazole resins, or phenol resins capable of being cured at low temperatures have been proposed as surface protective films or interlayer insulating films (for example, refer to Patent Documents 1 to 5).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2008-309885

[0008] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2007-57595

[0009] Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. 2008-076583

[0010] Patent Document 4: International Publication No. 2010 / 073948

[0011] Patent Document 5: Japanese Patent Application Laid-Open (JP-A) No. 2018-185480 SUMMARY

[0012] PROBLEMS TO BE SOLVED BY THE INVENTION

[0013] In a photosensitive resin composition for forming a surface protective film or an interlayer insulating film, in order to reduce stress, warpage, damage to semiconductor elements, a material having high reliability even when cured at a temperature of 250°C or lower is required, and further, from the viewpoint of environmental load, safety, and device constraints, a photosensitive material capable of being developed with an aqueous alkaline solution is strongly required. However, these materials are difficult to satisfy sufficient mechanical reliability in a package type having high stress, and cracks sometimes occur in the protective film or the insulating film.

[0014] An object of the present disclosure is to provide a simple sorting method of a photosensitive resin composition which forms a cured film capable of being developed with an aqueous alkaline solution, does not cause cracks and the like even when cured at a temperature of 250°C or lower, and has high mechanical reliability and thermal shock reliability, a photosensitive resin composition sorted by the sorting method, a manufacturing method of a patterned cured film using the photosensitive resin composition sorted by the sorting method, and a manufacturing method of a semiconductor device.

[0015] Means for solving the technical problem

[0016] One aspect of the present disclosure relates to a sorting method of a photosensitive resin composition, wherein a long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition to light at 100 to 2000 mJ / cm 2 A fatigue test of the long strip sample is performed under conditions where the set temperature is 25°C, the distance between the chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 100 MPa, and the photosensitive resin composition in which the number of times of stretching until the long strip sample is broken in the fatigue test is 100 cycles or more is sorted.

[0017] The fatigue test of the long strip sample can be performed under conditions where the set temperature is -55°C, the distance between the chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 120 MPa.

[0018] Another aspect of the present disclosure relates to a photosensitive resin composition, wherein a long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition to light at 100 to 2000 mJ / cm 2To prepare a long strip sample of a cured film with a thickness of 10 μm and a width of 10 mm, the resin film of the photosensitive resin composition is exposed to nitrogen and heat-treated at 150–250 °C for 1–3 hours. The long strip sample is then subjected to repeated tensile fatigue tests under the following conditions: a set temperature of 25 °C, a clamping distance of 20 mm, a test speed of 5 mm / min, and a repeated load stress of 100 MPa; or a set temperature of -55 °C, a clamping distance of 20 mm, a test speed of 5 mm / min, and a repeated load stress of 120 MPa. The number of tensile cycles until the long strip sample breaks is 100 or more.

[0019] Another aspect of this disclosure relates to a method for manufacturing a patterned resin film, comprising: a step of coating a photosensitive resin composition sorted using the above-described sorting method onto a portion or the entire surface of a substrate and drying it to form a resin film; a step of exposing at least a portion of the resin film; a step of developing the exposed resin film to form a patterned resin film; and a step of heating the patterned resin film.

[0020] Another aspect of this disclosure relates to a method for manufacturing a semiconductor device, wherein a patterned curing film formed by the above-described patterned curing film manufacturing method is provided as an interlayer insulating layer or a surface protective layer.

[0021] Invention Effects

[0022] According to this disclosure, a simple sorting method can be provided for a photosensitive resin composition that can be developed with an alkaline aqueous solution, does not crack even when cured at temperatures below 250°C, and forms a cured film with high mechanical and thermal shock reliability.

[0023] This disclosure provides a method for sorting photosensitive resin compositions, wherein when the photosensitive resin composition is used in a surface protective film or an interlayer insulating film, cracks caused by thermal shock, such as during temperature cycling tests, are not generated. The material is sorted through fatigue tests at 25°C or a previously unseen low temperature of -55°C. The resistance to fatigue failure at 25°C and -55°C is related to thermal shock reliability (package reliability). Through a simple and immediately evaluable fatigue test, the thermal shock reliability (package reliability) that would otherwise require time for sample preparation and evaluation can be easily evaluated in a short time. When the sorted photosensitive resin composition is used to manufacture a patterned curable film, a semiconductor device with excellent thermal shock reliability, such as that that does not crack during temperature cycling tests, can be manufactured. Attached Figure Description

[0024] Figure 1 This is a schematic cross-sectional view illustrating one embodiment of the manufacturing process of a semiconductor device.

[0025] Figure 2 is a schematic cross-sectional view illustrating an embodiment of a manufacturing process of a semiconductor device.

[0026] Figure 3 is a schematic cross-sectional view illustrating an embodiment of a manufacturing process of a semiconductor device.

[0027] Figure 4 is a schematic cross-sectional view illustrating an embodiment of a manufacturing process of a semiconductor device.

[0028] Figure 5 is a schematic cross-sectional view illustrating an embodiment of a manufacturing process of a semiconductor device.

[0029] Figure 6 is a schematic cross-sectional view illustrating an embodiment of an electronic component (semiconductor device).

[0030] Figure 7 is a schematic cross-sectional view illustrating an embodiment of an electronic component (semiconductor device). DETAILED DESCRIPTION

[0031] Hereinafter, a mode for carrying out the present disclosure will be explained in detail. However, the present application is not limited to the following embodiments. In the present specification, the term "process" does not only mean an independent process, but also includes a process as long as it achieves the intended function of the process, even if it cannot be distinguished from other processes. In the present specification, the term "layer" includes a structure in which a shape is formed in a part, in addition to a structure in which a shape is formed in an entire surface, when viewed in a plan view.

[0032] In the present specification, a numerical range indicated by "~" represents a range including the numerical values recited before and after "~" as the minimum value and the maximum value, respectively. In the present specification, the upper limit value or the lower limit value of a numerical range recited at a certain stage can be replaced with the upper limit value or the lower limit value of a numerical range recited at another stage. Also, in the present specification, the upper limit value or the lower limit value of a numerical range can be replaced with a value shown in the examples.

[0033] In the present specification, when the amount of each component in a composition is mentioned, the total amount of a plurality of substances corresponding to each component present in the composition is meant unless otherwise specified. In the present specification, "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid" corresponding thereto. The same applies to other similar expressions such as "(meth)acrylate".

[0034] [Sorting method of photosensitive resin composition]

[0035] In one way of the sorting method of the photosensitive resin composition of the present embodiment, the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 A long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition and performing heat treatment at 150 to 250°C for 1 to 3 hours under nitrogen. A fatigue test of repeatedly stretching the long strip sample is performed under conditions where the set temperature is 25°C, the distance between the jaws is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 100 MPa. The photosensitive resin composition is sorted in which the number of stretching until the long strip sample is broken in the fatigue test is 100 cycles or more.

[0036] In another way of the sorting method of the photosensitive resin composition of the present embodiment, the photosensitive resin composition is exposed at 100 to 2000 mJ / cm 2 A long strip sample of a cured film having a film thickness of 10 μm and a width of 10 mm is produced by exposing a resin film of the photosensitive resin composition and performing heat treatment at 150 to 250°C for 1 to 3 hours under nitrogen. A fatigue test of repeatedly stretching the long strip sample is performed under conditions where the set temperature is -55°C, the distance between the jaws is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 120 MPa. The photosensitive resin composition is sorted in which the number of stretching until the long strip sample is broken in the fatigue test is 100 cycles or more.

[0037] Hereinafter, the procedure of the sorting method of the photosensitive resin composition of the present embodiment is described in detail. First, the photosensitive resin composition is applied to a substrate and dried to form a resin film. The kind of the substrate is not particularly limited, and for example, a silicon wafer having a copper surface formed on the surface can be used. The photosensitive resin composition can be applied to the copper surface of the silicon wafer by a spin coater. A resin pattern is formed on the copper by exposing and developing the resin film. The exposure conditions of the resin film can be 500 to 1500 mJ / cm 2 or 800 to 1200 mJ / cm 2 The exposed resin film is developed by a developing solution such as an aqueous alkali solution to obtain a resin pattern. The cured film of the resin pattern can be formed by heating the resin pattern under nitrogen. The heating temperature of the resin pattern can be 160 to 230°C or 180 to 220°C, and the heating time can be 1.5 to 2.5 hours or 1.8 to 2.2 hours. A long strip sample (long strip cured film) for fatigue test measurement can be obtained by immersing the substrate having the cured film of the resin pattern formed therein in a copper etching solution.

[0038] In the sorting method of the photosensitive resin composition of the present embodiment, a fatigue test is performed on a long sample, and the photosensitive resin composition is sorted until the number of stretching times until the long sample breaks is 100 cycles or more. The fatigue test can be performed under either of the following (1) or (2).

[0039] Condition (1): The long sample is repeatedly stretched (0 to 100 MPa) under conditions where the set temperature is 25°C, the distance between the chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 100 MPa.

[0040] Condition (2): The long sample is repeatedly stretched (0 to 120 MPa) under conditions where the set temperature is -55°C, the distance between the chucks is 20 mm, the test speed is 5 mm / min, and the stress of the repeated load is 120 MPa.

[0041] By sorting the photosensitive resin composition whose number of stretching times until the long sample breaks in the fatigue test is 100 cycles or more, a cured film excellent in thermal shock reliability can be obtained, and thus cracks and the like can be reduced in the temperature cycle test of the semiconductor package. The number of stretching times until the long sample breaks in the fatigue test is defined as "fatigue resistance". The number of stretching times when the long sample breaks 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.

[0042] The photosensitive resin composition sorted according to the sorting method using the photosensitive resin composition of the present embodiment can suppress cracks in the resin layer even for a package in which the difference in linear expansion coefficient between copper and resin, stress derived from an organic material such as a sealing material, and warpage are large, and can produce a semiconductor device excellent in reliability to thermal shock due to temperature cycles even in a package in which stress is high.

[0043] The elongation at break of the long sample in the tensile test in which the long sample after 100-cycle fatigue test is stretched is preferably 10 to 60% under conditions where the set temperature is 25°C, the distance between the chucks is 20 mm, and the test speed is 5 mm / min. When the elongation of the cured film is 10% or more, stress is easily relaxed, and stress is concentrated on the semiconductor element or other organic components, and thus the reliability of the semiconductor package tends to be improved. When the elongation of the cured film is 60% or less, the cured film tends to be less likely to become weak at the time of temperature cycles. The elongation of the cured film is more preferably 15% or more from the aspect that stress can be relaxed more, and further preferably 20% or more from the aspect that crack resistance is improved.

[0044] As for the elongation, a tensile test was performed on the sample after the fatigue test under the conditions of 100 cycles of condition (1) or condition (2) by using a tensile tester with a special constant temperature tank (AG-1kNX plus) manufactured by Shimadzu Corporation, at a set temperature of -55°C, a distance between the grips of 20 mm, and a test speed of 5 mm / min, and the elongation at break was measured to obtain the elongation.

[0045] The yield stress of the long sample (cured film of the photosensitive resin composition) measured in the above tensile test is preferably 120 to 200 MPa. When the yield stress is 120 MPa or more, the cured film is less likely to be plastically deformed in a package where the stress is high, and thus is less likely to be adversely affected by repeated stress. When the yield stress of the cured film is 200 MPa or less, the impact resistance tends to be improved. From the viewpoint of maintaining the crack resistance after a thermal history, the yield stress of the cured film is more preferably 125 MPa or more, and further preferably 140 MPa or more.

[0046] As for the yield stress, the value of the stress at the intersection of the tangent line in the plot representing 5% elongation and the tangent line in the plot representing 15% elongation of the curve plotted with the horizontal axis as the elongation and the vertical axis as the stress was obtained as the yield stress.

[0047] In the above tensile test, the stress value at 1000 cycles of the approximate straight line obtained from three points plotted with the horizontal axis as the number of repeated tensile cycles at which the sample was broken and the vertical axis as the stress condition measured was obtained as the limit stress of the cured film of the photosensitive resin composition, by measuring under three different stress conditions where the number of repeated tensile cycles became 2 to 1000. The limit stress of the cured film is preferably 120 MPa or more, and more preferably 125 MPa or more from the viewpoint of maintaining the crack resistance after a thermal history.

[0048] The Young's modulus of the long sample measured in the above tensile test is preferably 0.5 to 2.8 GPa. When the Young's modulus of the cured film is 0.5 GPa or more, the cured film is less likely to be deformed when a stress is applied, and it becomes easier to suppress stress concentration on a material with a high Young's modulus mounted on a semiconductor package. When the Young's modulus of the cured film is 2.8 GPa or less, stress is alleviated by the cured film, and it becomes less likely to cause damage to a semiconductor element. The Young's modulus of the cured film is more preferably 1.0 to 2.7 GPa, and further preferably 1.4 to 2.6 GPa.

[0049] In the above tensile test, the Young's modulus can be calculated from the slope in the elongation range of 0 to 5% of the curve plotted with the horizontal axis as the elongation and the vertical axis as the stress.

[0050] The glass transition temperature (Tg) of the cured film of the photosensitive resin composition of the present embodiment is preferably 150°C or higher, more preferably 170°C or higher, and further preferably 180°C or higher. By having a Tg of 150°C or higher, the stress at the time of temperature change in a temperature cycle test or the like can be reduced. The upper limit of the Tg of the cured film can be 300°C or lower.

[0051] With respect to the Tg, the viscoelasticity of the above-mentioned long sample can be measured using a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd. under conditions of a distance of 20 mm between the grips, a frequency of 10 Hz, a temperature increase rate of 5°C / min, and a temperature range of 40 to 260°C, and the temperature at which the maximum value of tan δ is obtained is taken as the glass transition temperature.

[0052] The linear expansion coefficient of the cured film of the photosensitive resin composition of the present embodiment is preferably 20 to 100 ppm / °C (20 x 10 -6 to 100 x 10 -6 / °C). By having a linear expansion coefficient of 100 ppm / °C or lower, the stress at the time of temperature change can be suppressed. When the linear expansion coefficient of the cured film is 20 ppm / °C or higher, the occurrence of cracks can be easily suppressed.

[0053] The adhesion rate of the cured film of the photosensitive resin composition of the present embodiment to an electrolytic copper-plated substrate is preferably 75% or higher. When the adhesion rate is 75% or higher, the cured film peels from the electrolytic copper-plated pattern serving as the base when stress is applied, and the stress tends to concentrate on the material having a high adhesion rate to the electrolytic copper-plated pattern mounted on the semiconductor package. The higher the adhesion rate, the better, and more preferably, the adhesion rate is 90% or higher, and further preferably, the adhesion rate is 95% or higher, and particularly preferably, the adhesion rate is 100%.

[0054] The adhesion rate can be measured in the following order. First, the photosensitive resin composition is applied to an electrolytic copper-plated substrate using a spin coater so that the film thickness after curing is 10 μm, and heating is performed under a nitrogen atmosphere at 200°C for 2 hours to form a cured film. Next, after repeating a temperature cycle test in which the temperature is changed with -65°C as the starting temperature and the ending temperature, 200 times, to the cured film under an atmospheric pressure air atmosphere at a temperature of -65 to 150°C with a stop time of 15 minutes, the cured film is cut into a grid shape using a cross-cut method prescribed in JIS K 5600-5-6. A tape peeling test is performed on the cured film cut into a grid shape, and the proportion of the lattice (cured film) adhered to the electrolytic copper-plated substrate (adhesion rate) is calculated.

[0055] The photosensitive resin composition of the embodiment has a number of stretching cycles of 100 cycles or more until the long sample is broken when the above fatigue test is performed. The photosensitive resin composition can be either a positive photosensitive resin composition or a negative photosensitive resin composition. The photosensitive resin composition can contain, for example, (A) an alkali-soluble resin, (B) a thermosetting resin, and (C) a photosensitive agent. Hereinafter, each component that the photosensitive resin composition can contain will be described in detail.

[0056] ((A) Component: Alkali-soluble Resin)

[0057] From the viewpoint of improving alkali developability, the photosensitive resin composition of the embodiment can contain, as the (A) component, an alkali-soluble resin. In the present specification, the alkali-soluble resin refers to a resin that is soluble in an aqueous alkali solution (developer). In addition, the aqueous alkali solution is an alkali solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution. Generally, a TMAH aqueous solution having a concentration of 2.38% by mass is used at the time of development. For example, it can be confirmed that the (A) component is soluble in the alkali developer as follows.

[0058] 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 μm. The coating film is immersed in any one of a TMAH aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution at 20 to 25°C. As a result, when the coating film can be uniformly dissolved, it can be considered that the resin is soluble in the alkali developer.

[0059] As the (A) component, there is no particular limitation as long as it is a component that is dissolved in a 2.38% by mass TMAH aqueous solution, and a compound having a phenolic hydroxyl group or a carboxyl group is preferred.

[0060] As the compound having a phenolic hydroxyl group, for example, a polyimide resin, a polybenzoxazole resin, a polyamide resin, a phenol-formaldehyde condensate, i.e., a novolak resin, a cresol-formaldehyde condensate novolak resin, a phenol-naphthol / formaldehyde condensate novolak resin, a polyhydroxystyrene or a copolymer thereof, a phenol-xylene glycol condensate resin, a cresol-xylene glycol condensate resin, a phenol-dicyclopentadiene condensate resin, and an acrylic polymer having a phenolic hydroxyl group can be given.

[0061] As the acrylic polymer having a phenolic hydroxyl group, there is no particular limitation, and an acrylic polymer represented by the following general formula (1) can be used. In formula (1), R1represents a hydrogen atom or a methyl group.

[0062] [Chemical Formula 1]

[0063]

[0064] From the viewpoint of reducing the pattern formability and voids at the time of thermocompression bonding, the phenolic hydroxyl equivalent weight of the acrylic polymer having a phenolic hydroxyl group is preferably 200 to 700 g / eq.

[0065] The acrylic polymer having a phenolic hydroxyl group can be a copolymer having a structural unit represented by formula (1) together with a structural unit other than the structural unit represented by formula (1) (hereinafter, simply referred to as "other structural unit"). The other structural unit is a structural unit derived from a monomer capable of copolymerizing with the monomer having the structural unit represented by formula (1). The monomer having the other structural unit is not particularly limited, but a (meth) acrylate compound or a vinyl compound can be used.

[0066] As the monomer having the other structural unit, for example, a methyl acrylate, an ethyl acrylate, a propyl acrylate, a butyl acrylate, an octyl acrylate, a methoxymethyl acrylate, a methoxyethyl acrylate, an ethoxyethyl acrylate, a butoxyethyl acrylate, a methoxyethoxyethyl acrylate, an acrylic acid, a methacrylic acid, a hydroxyethyl acrylate, a hydroxymethyl methacrylate, an acrylonitrile, a methacrylonitrile, an ethyl acrylonitrile, a dihydroxydicyclopentenyl acrylate, a dihydroxydicyclopentenyl methacrylate, a dihydroxydicyclopentenyl itaconate, a dihydroxydicyclopentenyl maleate, a dihydroxydicyclopentenyl fumarate, a dihydroxydicyclopentenyloxyethyl acrylate, a dihydroxydicyclopentenyloxyethyl methacrylate, a dihydroxydicyclopentenyloxyethyl itaconate, a dihydroxydicyclopentenyloxyethyl maleate, a dihydroxydicyclopentenyloxyethyl fumarate, a vinyl methacrylate, a vinyl acrylate, a 1,1-dimethylpropenyl methacrylate, a 1,1-dimethylpropenyl acrylate, a 3,3-dimethylbutenyl methacrylate, a 3,3-dimethylbutenyl acrylate, a divinyl itaconate, a divinyl maleate, a divinyl fumarate, a dicyclopentadiene, a methyl dicyclopentadiene, an ethylidenenorbornene, a 1,1-dimethylpropenyl methacrylate, a 1,1-dimethylpropenyl acrylate, a 3,3-dimethylbutenyl methacrylate, a 3,3-dimethylbutenyl acrylate, a vinyl 1,1-dimethylpropenyl ether, a vinyl 3,3-dimethylbutenyl ether, a 1-acryloyloxy-1-phenyl ethylene, a 1-acryloyloxy-2-phenyl ethylene, a 1-methacryloyloxy-1-phenyl ethylene, and a 1-methacryloyloxy-2-phenyl ethylene can be exemplified.

[0067] The (A) component can include a compound having a carboxyl group. As the compound having a carboxyl group, there is no particular limitation, but it is preferable to use an acrylic polymer having a carboxyl group in the side chain.

[0068] As component (A), an alkali-soluble resin with a Tg of 150°C or higher and an alkali-soluble resin with a Tg of 120°C or lower can be mixed. By configuring it in this way, a cured film with superior reliability can be obtained.

[0069] When mixing an alkali-soluble resin (A1) with a Tg of 150°C or higher and an alkali-soluble resin (A2) with a Tg of 120°C or lower, it is preferable to blend (A2) at 5 to 30 parts by mass relative to 100 parts by mass of (A1). When the blending amount of (A2) is 5 parts by mass or more, the elongation of the cured film is impaired and the fatigue resistance tends to decrease; when it is 30 parts by mass or less, the strength of the cured film is impaired and the fatigue resistance tends to decrease.

[0070] The Tg of component (A) is the peak temperature of tanδ when the substance obtained by film formation of component (A) is measured using a viscoelastic analyzer (product name "RSA-2", manufactured by Rheometric Scientific) at a heating rate of 5℃ / min, a frequency of 1Hz, and a measurement temperature of -150 to 300℃.

[0071] The weight-average molecular weight (Mw) of component (A) is preferably controlled in the range of 2,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 80,000. In particular, the Mw of the alkali-soluble resin in (A1) is preferably 2,000 to 50,000, more preferably 4,000 to 30,000 from the viewpoint of reliability, and even more preferably 2,000 to 30,000 from the viewpoint of resolution during pattern formation. Furthermore, the Mw of the alkali-soluble resin in (A2) is preferably 10,000 to 100,000, more preferably 15,000 to 100,000 from the viewpoint of reliability, and even more preferably 15,000 to 70,000 from the viewpoint of resolution during pattern formation.

[0072] In this specification, Mw is a value determined by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. As the measuring apparatus, for example, a high-performance liquid chromatograph (product name "C-R4A", manufactured by Shimadzu Corporation) can be used.

[0073] From the viewpoint of further improving resistance to fatigue damage, component (A) may contain an alkali-soluble resin having imide groups. As an alkali-soluble resin having imide groups, an acrylic polymer polymerized with (meth)acrylate compounds having imide groups is preferred from the perspective of being able to adjust the concentration of imide groups arbitrarily. Alkali-soluble polyimides can also be used as alkali-soluble resins having imide groups. From the viewpoint of resolution, it is preferable to use an alkali-soluble resin having imide groups in combination with a phenolic varnish resin or a phenolic resin.

[0074] The alkali-soluble resin having an imide group can be a copolymer of a (meth)acrylate compound having an imide group and a (meth)acrylate compound having a phenolic hydroxyl or carboxyl group. Examples of (meth)acrylate compounds having an imide group include N-acryloyloxyethyl hexahydrophthalimide and N-methacryloyloxyethyl hexahydrophthalimide. Based on the proportion of structural units of the (meth)acrylate compound having an imide group, taking into account all monomer units constituting the alkali-soluble resin having an imide group, the proportion is preferably 10% by mass or more from the viewpoint of improving the toughness of the cured film, more preferably 20% by mass or more from the viewpoint of sufficiently imparting resistance to fatigue damage, and preferably 60% by mass or less from the viewpoint of not impairing alkali solubility.

[0075] The content of the alkali-soluble resin with imide groups, based on the total amount of component (A), is preferably 10% by mass or more in terms of improving the toughness of the cured film, more preferably 20% by mass or more in terms of suppressing deterioration during thermal processes, and even more preferably 30% by mass or more in terms of providing sufficient resistance to fatigue damage.

[0076] (A) The composition may include alkali-soluble resins with imide groups and alkali-soluble resins without imide groups. This allows for a high degree of balance between the microprocessability of the photosensitive resin composition during development and the fatigue resistance of the cured film.

[0077] The content of the alkali-soluble resin with imide groups, based on the total amount of solid components contained in the photosensitive resin composition, is preferably 5% by mass or more in terms of improving the strength of the cured film, more preferably 10% by mass or more in terms of improving fatigue strength, further preferably 20% by mass or more in terms of maintaining sufficient fatigue strength even after thermal degradation of the cured film, further preferably 30% by mass or more in terms of improving the toughness of the cured film, and preferably 80% by mass or less in terms of maintaining the microprocessability of the photosensitive resin composition during development. The alkali-soluble resin with imide groups contained in the photosensitive resin composition is particularly preferably 30 to 80% by mass.

[0078] ((B) Component: Thermosetting resin)

[0079] The photosensitive resin composition of this embodiment preferably comprises (B) a thermosetting resin. Examples of the (B) thermosetting resin include acrylate resins, epoxy resins, cyanate ester resins, maleimide resins, allylimide resins, phenolic resins, urea resins, melamine resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, triallyl cyanate resins, polyisocyanate resins, resins containing tris(2-hydroxyethyl) isocyanurate, resins containing triallyl trimellitate, and thermosetting resins synthesized from cyclopentadiene. From the viewpoint of resolution, insulation reliability, and adhesion to metals, the thermosetting resin is more preferably a compound having any one of hydroxymethyl, alkoxyalkyl, and glycidyl groups.

[0080] By incorporating a glycidyl compound as component (B) into a photosensitive resin composition, and then heating and curing the patterned resin film, a bridging structure is formed by reacting with component (A). This prevents embrittlement and melting of the cured film. Conventionally known compounds can be used as the glycidyl compound. Examples of glycidyl compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic varnish epoxy resin, cresol phenolic varnish epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin, and polyalkylene glycol diglycidyl ether.

[0081] In terms of solubility relative to alkaline aqueous solution and physical properties of cured film, the amount of a compound containing glycidyl group incorporated into the photosensitive resin composition is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, relative to 100 parts by mass of component (A).

[0082] ((C) Ingredient: Photosensitizer)

[0083] The photosensitive resin composition of this embodiment preferably includes a (C) photosensitizer. As the (C) photosensitizer, a photoradical polymerization initiator that generates free radicals by light irradiation or a photoacid generator that generates acids by light irradiation can be used.

[0084] Examples of photoradical polymerization initiators include alkylphenyl ketone-based photopolymerization initiators, acylphosphine-based photopolymerization initiators, intramolecular hydrogen-free photopolymerization initiators, and cationic photopolymerization initiators. These photopolymerization initiators are available from IGM Resins, such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 379EG, Omnirad 819, Omnirad MBF, Omnirad TPO, and Omnirad 784; and from BASF, such as Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04. Depending on the purpose and application, one of these photoradical polymerization initiators can be used alone, or two or more of these photoradical polymerization initiators can be used in combination.

[0085] Photoacid-generating agents have the function of generating acid through light irradiation and increasing the solubility of the irradiated portion in alkaline aqueous solutions. Examples of photoacid-generating agents include o-quinone diazide compounds, aryl diazonium salts, diaryliodonium salts, and triaryl sulfonium salts. Among these, o-quinone diazide compounds are preferred in terms of high sensitivity. For example, compounds obtained by condensing o-quinone diazidesulfonyl chloride with hydroxyl compounds, amino compounds, etc., in the presence of a dehydrochlorinating agent can be used. The reaction temperature can be 0–40°C, and the reaction time can be 1–10 hours.

[0086] Examples of ortho-quinone diazidesulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride.

[0087] Examples of hydroxyl compounds include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Benzyl ketone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindo[2,1-a]indene, tris(4-hydroxyphenyl)methane and tris(4-hydroxyphenyl)ethane.

[0088] Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 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(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)hexafluoropropane.

[0089] From the viewpoint of reactivity in the synthesis of ortho-quinone diazide compounds and from the viewpoint of exposure of resin films within an appropriate absorption wavelength range, compounds obtained by condensing 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane with 1-naphthoquinone-2-diazido-5-sulfonyl chloride, and compounds obtained by condensing tris(4-hydroxyphenyl)methane or tris(4-hydroxyphenyl)ethane with 1-naphthoquinone-2-diazido-5-sulfonyl chloride are preferred.

[0090] Examples of dehydrochloric acid removers include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine. Examples of reaction solvents include dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and N-methylpyrrolidone.

[0091] Preferably, the o-quinone diazidesulfonyl chloride is blended with the hydroxyl compound and / or amino compound in such a manner that the total number of moles of hydroxyl and amino groups relative to 1 mole of o-quinone diazidesulfonyl chloride is 0.5 to 1 mole. The preferred blending ratio of the dehydrochlorinating agent to the o-quinone diazidesulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 molar equivalents.

[0092] In terms of the permissible range of the dissolution rate difference and sensitivity between the exposed and non-exposed areas, the content of component (C) is preferably 3 to 100 parts by mass relative to 100 parts by mass of component (A), more preferably 5 to 50 parts by mass, and even more preferably 5 to 30 parts by mass.

[0093] ((D) Component: Low molecular weight compound with phenolic hydroxyl groups)

[0094] The photosensitive resin composition of the embodiment can contain a low-molecular-weight compound having phenolic hydroxyl groups. The low-molecular-weight compound having phenolic hydroxyl groups is used to increase the dissolution rate of the exposed portion during development with an alkaline aqueous solution and to improve sensitivity. By containing component (D), when the resin film after pattern formation is heated and cured, component (D) reacts with component (A) to form a bridging structure. This prevents embrittlement and melting of the cured film.

[0095] The molecular weight of component (D) is preferably 2000 or less. Considering the balance between solubility in alkaline aqueous solution and photosensitivity with the properties of the cured film, the molecular weight (Mn) is preferably 94 to 2000, more preferably 108 to 2000, and even more preferably 108 to 1500.

[0096] As a low molecular weight compound with phenolic hydroxyl groups, conventionally known compounds can be used, but the compound represented by the following general formula (2) has an excellent balance between the dissolution promotion effect on the exposed part and the melting effect during resin film curing, and is therefore particularly preferred.

[0097] [Chemical Formula 2]

[0098]

[0099] In formula (2), X represents a single bond or a divalent organic group, and R 1 R 2 R 3 and R 4 Each of the following can be used to independently represent a hydrogen atom or a monovalent organic group: s and t can be used to independently represent integers from 1 to 3; u and v can be used to independently represent integers from 0 to 4.

[0100] In formula (2), the compound in which X is a single bond is a biphenyl (dihydroxybiphenyl) derivative. Examples of divalent organic groups represented by X include alkylene groups with 1 to 10 carbon atoms such as methylene, ethylene, and propylene; alkylene groups with 2 to 10 carbon atoms such as ethylene; aryl groups with 6 to 30 carbon atoms such as alkylene; groups in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced by halogen atoms such as fluorine atoms; sulfonyl groups; carbonyl groups; ether bonds; thioether bonds; and amide bonds. Among these, divalent organic groups represented by the following general formula (3) are preferred.

[0101] [Chemical Formula 3]

[0102]

[0103] In formula (3), X' represents a single bond, alkylene (e.g., alkylene with 1 to 10 carbon atoms), alkylene (e.g., alkylene with 2 to 10 carbon atoms), a group in which some or all of these hydrogen atoms are replaced by halogen atoms, sulfonyl, carbonyl, oxy, thio or amide, R” represents a hydrogen atom, hydroxyl, alkyl or haloalkyl, g represents an integer from 1 to 10, and multiple R” can be the same as each other or different from each other.

[0104] In terms of the permissible range of the ratio of development time to residual film in non-exposed areas and the characteristics of the cured film, the amount of low molecular weight compound having phenolic hydroxyl groups in addition to 100 parts by mass of component (A) is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 25 parts by mass.

[0105] (Other ingredients)

[0106] In addition to the above, the photosensitive resin composition of the embodiments may also contain compounds that generate acid by heating, elastomers, solubilizers, solubilizers, coupling agents, solvents, surfactants, leveling agents, and other components.

[0107] (Compounds that produce acids upon heating)

[0108] The photosensitive resin composition of the embodiment can include a compound that generates acid upon heating. By using a compound that generates acid upon heating, acid can be generated when the patterned resin film is heated, thereby promoting the reaction of components (A), (B), and (D) – i.e., the thermal bridging reaction – and thus improving the heat resistance of the patterned cured film. Furthermore, the compound that generates acid upon heating also generates acid upon light irradiation, thus increasing the solubility of the exposed portion in the alkaline aqueous solution. As a result, the difference in solubility between the non-exposed and exposed portions relative to the alkaline aqueous solution becomes larger, and the resolution is further improved.

[0109] Compounds that generate acids upon heating are preferably compounds that generate acids by heating to 50–250°C. Examples of compounds that generate acids upon heating include onium salts and other salts formed from strong acids and bases, as well as imide sulfonates.

[0110] Examples of onium salts include diaryl iodonium salts such as aryl diazonium salts and diphenyliodonium salts; di(alkylaryl) sulfonium salts such as diaryl iodonium salts and di(tert-butylphenyl) sulfonium salts; trialkyl sulfonium salts such as trimethyl sulfonium salts; dialkyl monoaryl sulfonium salts such as dimethylphenyl sulfonium salts; diaryl monoalkyl sulfonium salts such as diphenylmethyl sulfonium salts; and triaryl sulfonium salts. Among these, the preferred salts are di(tert-butylphenyl) sulfonate of p-toluenesulfonic acid, di(tert-butylphenyl) sulfonate of trifluoromethanesulfonic acid, trimethyl sulfonate of trifluoromethanesulfonic acid, dimethyl phenyl sulfonate of trifluoromethanesulfonic acid, diphenyl methyl sulfonate of trifluoromethanesulfonic acid, di(tert-butylphenyl) sulfonate of nonafluorobutanesulfonic acid, diphenyl iodomonium salt of camphorsulfonic acid, diphenyl iodomonium salt of ethanesulfonic acid, dimethyl phenyl sulfonate of benzenesulfonic acid, and diphenyl methyl sulfonate of toluenesulfonic acid.

[0111] In addition to the onium salts mentioned above, other salts formed from strong acids and bases, such as pyridinium salts, can also be used as salts formed from strong acids and bases. Examples of strong acids include aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; perfluoroalkyl sulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid; and alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. Examples of bases include alkylpyridines such as pyridine and 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated N-alkylpyridines.

[0112] Examples of imide sulfonates include naphthylimide sulfonate and phthalimide sulfonate.

[0113] In addition to the compounds mentioned above, compounds that generate acids by heating can also be used as compounds having a structure represented by the following general formula (4) or compounds having a sulfonamide structure represented by the following general formula (5).

[0114] R 5 R 6 C = NO - SO2 - R 7 (4)

[0115] -NH-SO2-R 8 (5)

[0116] In equation (4), R 5 For example, cyano, R 6 For example, methoxyphenyl, phenyl, etc., R 7 Examples include aryl groups such as p-methylphenyl, phenyl, methyl, ethyl, isopropyl, trifluoromethyl, and nonafluorobutyl.

[0117] In equation (5), R 8 Examples include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as methylphenyl and phenyl; perfluoroalkyl groups such as trifluoromethyl and nonafluorobutyl. Examples of groups that bond to the N atom of the sulfonamide structure represented by general formula (5) include 2,2'-bis(4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(4-hydroxyphenyl)propane, and di(4-hydroxyphenyl) ether.

[0118] The amount of admixture used when using a compound that generates an acid by heating can be 0.1 to 30 parts by mass, 0.2 to 20 parts by mass, or 0.5 to 10 parts by mass relative to 100 parts by mass of component (A).

[0119] (elastomer)

[0120] In addition to the above, the photosensitive resin composition of the embodiments may contain an elastomer component. The elastomer is used to impart flexibility to the cured form of the photosensitive resin composition. Conventionally known elastomers can be used as elastomers, but the Tg of the polymer constituting the elastomer is preferably below 20°C.

[0121] Examples of elastomers include styrene-based elastomers, olefin-based elastomers, amine ester elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers can be used alone or in combination of two or more.

[0122] Relative to 100 parts by mass of component (A), the amount of elastomer used can be 1 to 50 parts by mass or 5 to 30 parts by mass. When the amount of elastomer used is 1 part by mass or more, the thermal shock resistance of the cured film tends to improve. When it is 50 parts by mass or less, the resolution and the heat resistance of the obtained cured film are not easily reduced, and thus the compatibility and dispersibility with other components tend to be less reduced.

[0123] (Solubility accelerator)

[0124] By incorporating a solubility accelerator into the photosensitive resin composition, the dissolution rate of the exposed portion during development with an alkaline aqueous solution can be increased, thereby improving sensitivity and resolution. Conventionally known solubility accelerators can be used as solubility accelerators. Examples of solubility accelerators include compounds having carboxyl, sulfonic acid, or sulfonamide groups. The amount of solubility accelerator used can be determined based on the dissolution rate relative to the alkaline aqueous solution; for example, it can be set to 0.01 to 30 parts by mass relative to 100 parts by mass of component (A).

[0125] (Dissolution Inhibitor)

[0126] Dissolution inhibitors are compounds that inhibit the solubility of component (A) in alkaline aqueous solutions, used to control residual film thickness, development time, and contrast. Examples of dissolution inhibitors include diphenyliodonitrate, bis(p-tert-butylphenyl)iodonitrate, diphenyliodobromide, diphenyliodochloride, and diphenyliodomonium iodide. In terms of the permissible range of sensitivity and development time, the amount of dissolution inhibitor used relative to 100 parts by weight of component (A) can be 0.01–20 parts by weight, 0.01–15 parts by weight, or 0.05–10 parts by weight.

[0127] (Coupled agent)

[0128] By incorporating a coupling agent into a photosensitive resin composition, the adhesion between the formed patterned cured film and the substrate can be improved. Examples of coupling agents include organosilane compounds and aluminum chelate compounds.

[0129] Examples of organosilane compounds include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, urea-formaldehyde-propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilane, n-propylmethylphenylsilane, isopropylmethylphenylsilane, n-butylmethylphenylsilane, isobutylmethylphenylsilane, tert-butylmethylphenylsilane, ethyl-n-propylphenylsilane, ethyl-isopropylphenylsilane, and n-butylethylphenylsilane. Alcohols, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis(trihydroxysilane)benzene, 1,4-bis(methyldihydroxysilane)benzene, 1,4-bis(ethyldihydroxysilane)benzene, 1,4-bis(propyldihydroxysilane)benzene, 1,4-bis(butyldihydroxysilane)benzene, 1,4-bis(dimethylhydroxysilane)benzene, 1,4-bis(diethylhydroxysilane)benzene, 1,4-bis(dipropylhydroxysilane)benzene and 1,4-bis(dibutylhydroxysilane)benzene.

[0130] The amount of coupling agent used can be 0.1 to 20 parts by mass or 0.5 to 10 parts by mass relative to 100 parts by mass of component (A).

[0131] (surfactant or leveling agent)

[0132] By incorporating surfactants or leveling agents into photosensitive resin compositions, coatability can be further improved. Specifically, for example, by including surfactants or leveling agents, streaks (uneven film thickness) can be further prevented, or developability can be further improved. Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, and polyoxyethylene octylphenol ether. Commercially available surfactants or leveling agents include MEGAFACE F171, F173, R-08 (manufactured by DICCORPORATION), FLUORAD FC430, FC431 (manufactured by Sumitomo 3MLimited), and organosiloxane polymers KP341, KBM303, KBM403, and KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0133] The amount of surfactant or leveling agent used in a mixture relative to 100 parts by weight of component (A) can be 0.001 to 5 parts by weight or 0.01 to 3 parts by weight.

[0134] (solvent)

[0135] Photosensitive resin compositions, by containing solvents for dissolving or dispersing the components, can be easily coated onto a substrate, thereby achieving effects such as forming a coating film of uniform thickness.

[0136] Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, diphenylethylene acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methylpentyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. One solvent can be used alone or in combination of two or more.

[0137] There is no particular limitation on the amount of solvent incorporated, but it is preferred to adjust the proportion of solvent in the photosensitive resin composition to be 20 to 90 by mass.

[0138] The photosensitive resin composition of this embodiment can be developed using alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). By using the photosensitive resin composition of this embodiment, resist patterns with good shape and excellent adhesion and heat resistance can be formed with sufficiently high sensitivity and resolution.

[0139] [Manufacturing method of patterned curing film]

[0140] The method for manufacturing the patterned resin film (resist pattern) according to this embodiment includes: a step of coating a portion or the entire surface of a substrate with the above-described photosensitive resin composition and drying it to form a resin film (coating / drying (film formation) step); a step of exposing at least a portion of the resin film (exposure step); a step of developing the exposed resin film to form a patterned resin film (development step); and a step of heating the patterned resin film (photosensitive resin film) (heat treatment step). Each step will be described below.

[0141] (Coating / Drying (Film Forming) Process)

[0142] First, the photosensitive resin composition of this embodiment is coated onto a substrate and dried to form a resin film. In this process, the photosensitive resin composition is spin-coated onto a substrate such as a glass substrate, semiconductor, metal oxide insulator (e.g., TiO2, SiO2, etc.), or silicon nitride using a spin coater to form a coating. The substrate with the coating formed is dried using a hot plate, oven, or similar equipment. The drying temperature and drying time are not particularly limited, but can be 80–140°C and 1–7 minutes. Thus, a photosensitive resin film is formed on the substrate.

[0143] (Exposure process)

[0144] Next, in the exposure process, the resin film formed on the substrate is irradiated with active light such as ultraviolet light, visible light, or radiation through a mask. In the above-mentioned photosensitive resin composition, component (A) has higher transparency relative to the i-line, so irradiation with the i-line is preferred. In addition, after exposure, post-exposure heating (PEB) can be performed as needed. The preferred post-exposure heating temperature is 70 to 140°C, and the post-exposure heating time is 1 to 5 minutes.

[0145] (Developing process)

[0146] In the developing process, the exposed portion of the resin film after the exposure process is removed using a developing solution, and the resin film is patterned to obtain a patterned resin film. As the developing solution, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH) are preferred. The alkalinity of these aqueous solutions can be 0.1 to 10% by mass. Alcohols or surfactants can also be added to the above developing solutions. These can be mixed in the range of 0.01 to 10 parts by mass or 0.1 to 5 parts by mass relative to 100 parts by mass of the developing solution, respectively. When developing using the developing solution, the developing solution is applied to the resin film using methods such as spray development, mist development, immersion development, or pit development, and the film is placed at 18 to 40°C for 30 to 360 seconds. After placement, the patterned resin film is cleaned by washing with water and rotary drying.

[0147] (Heat treatment process)

[0148] Next, in the heat treatment process, a patterned resin film (resist pattern) can be formed by heat treatment. In order to fully prevent heat-induced damage to electronic devices, the heating temperature in the heat treatment process can be below 250°C, below 225°C, or 140–200°C.

[0149] For example, ovens such as quartz tube furnaces, hot plates, rapid annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces can be used for heat treatment. Furthermore, either atmospheric or inert atmospheres such as nitrogen can be selected, but nitrogen is preferred as it prevents oxidation of the pattern. Since the heating temperature range described above is lower than conventional heating temperatures, damage to the substrate and electronic devices can be minimized. Therefore, by using the pattern curing film manufacturing method of this embodiment, electronic devices can be manufactured with high yield. Furthermore, it contributes to energy saving in the process. In addition, according to the photosensitive resin composition of this embodiment, the volume shrinkage (curing shrinkage) during the heat treatment process seen in photosensitive polyimides and the like is small, thus preventing a decrease in dimensional accuracy.

[0150] The heating time in the heat treatment process only needs to be sufficient to cure the photosensitive resin composition, but considering the balance with work efficiency, it is preferable to be about 5 hours or less.

[0151] In addition to the ovens mentioned above, microwave curing devices or frequency conversion microwave curing devices can also be used for heat treatment. By using these devices, it is possible to effectively heat only the resin film while keeping the temperature of the substrate and electronic devices at the desired temperature (e.g., below 200°C).

[0152] In a variable frequency microwave curing apparatus, microwaves are pulsed while the frequency is changed, thus preventing fixed-wave heating and enabling uniform heating of the substrate surface. Furthermore, when the substrate includes electronic components such as metal wiring (described later), pulsed microwave irradiation while changing the frequency prevents metal-borne discharges, protecting the electronic components from damage. Additionally, when using variable frequency microwave heating, even with a lower curing temperature compared to using an oven, the physical properties of the cured film are unlikely to deteriorate (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)).

[0153] The frequency of the variable-frequency microwave is in the range of 0.5 to 20 GHz, but in practice it can be in the range of 1 to 10 GHz or 2 to 9 GHz. Furthermore, although it is desirable for the frequency of the irradiated microwave to change continuously, in practice the irradiation is carried out by gradually changing the frequency. In this case, if the irradiation time of the single-frequency microwave is minimized, it is less likely to produce fixed waves, discharges from metals, etc. Therefore, the irradiation time of the microwave is preferably less than 1 millisecond, and more preferably less than 100 microseconds.

[0154] The output of the irradiated microwaves varies depending on the size of the device or the amount of the object being heated, but it is generally in the range of 10 to 2000W. In actual use, it can be 100 to 1000W, 100 to 700W, or 100 to 500W. When the output is above 10W, it is easy to heat the object in a short time, while when it is below 2000W, it is less likely to cause a rapid temperature rise.

[0155] Microwave irradiation is preferably performed in a pulsed on / off manner. Pulsed microwave irradiation maintains the set heating temperature and avoids damage to the cured film and substrate, which is preferable in this respect. The duration of one pulse of microwave irradiation varies depending on the conditions, but is preferably less than approximately 10 seconds.

[0156] According to the above-described method for manufacturing patterned curable films, patterned curable films with good heat resistance can be obtained with sufficiently high sensitivity and resolution. The patterned curable film of this embodiment can be used as an interlayer insulating layer or a surface protective layer for semiconductor devices.

[0157] [Semiconductor device manufacturing process]

[0158] As an example of the method for manufacturing the patterned film (resist pattern) of this embodiment, the manufacturing process of the semiconductor device will be described with reference to the accompanying drawings. Figures 1-5 This is a schematic cross-sectional view illustrating one embodiment of the manufacturing process of a semiconductor device having a multilayer wiring structure.

[0159] First, prepare Figure 1 The structure 100 shown includes: a semiconductor substrate 1 such as a Si substrate, having circuit elements; a protective film 2 such as a silicon oxide film, having a predetermined pattern exposing the circuit elements and covering the semiconductor substrate 1; a first conductor layer 3 formed on the exposed circuit elements; and an interlayer insulating layer 4 formed on the protective film 2 and the first conductor layer 3 by spin coating or the like, and formed of a polyimide resin or the like.

[0160] Next, by forming a photosensitive resin layer 5 with a window portion 6A on the interlayer insulating layer 4, a photosensitive resin layer 5 is obtained. Figure 2The structure 200 shown. For example, a photosensitive resin layer 5 is formed by coating a photosensitive resin such as chlorinated rubber, phenolic varnish, polyhydroxystyrene, or polyacrylate using a spin coating method. The window 6A is formed by exposing the interlayer insulating layer 4 in a specified area using a known photogravure technique.

[0161] After etching the interlayer insulating layer 4 to form the window 6B, the photosensitive resin layer 5 is removed to obtain... Figure 3 The structure 300 is shown. The interlayer insulating layer 4 can be etched using a dry etching method employing gases such as oxygen or carbon tetrafluoride. This etching selectively removes the portion of the interlayer insulating layer 4 corresponding to the window 6A, resulting in an interlayer insulating layer 4 with the window 6B exposed. Next, the photosensitive resin layer 5 is removed using an etching solution that does not etch the first conductor layer 3 exposed from the window 6B, but only etches the photosensitive resin layer 5.

[0162] Additionally, a second conductor layer 7 is formed in the portion corresponding to window 6B to obtain Figure 4 The structure 400 shown. A known photolithography technique can be used to form the second conductor layer 7. This allows for an electrical connection between the second conductor layer 7 and the first conductor layer 3.

[0163] Finally, a surface protective layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain... Figure 5 The semiconductor device 500 shown is described above. In this embodiment, the surface protective layer 8 is formed as follows: First, the photosensitive resin composition of the above embodiment is coated onto the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and then dried to form a resin film. Next, the resin film is patterned by developing with an alkaline aqueous solution after being irradiated with light through a mask in which a pattern corresponding to the window 6C is drawn in a predetermined area. Afterward, the resin film is cured by heating to form a film as the surface protective layer 8. This surface protective layer 8 is a surface protective layer that protects the first conductor layer 3 and the second conductor layer 7 from external stress, α lines, etc., and the resulting semiconductor device 500 has excellent reliability.

[0164] Furthermore, while the above embodiment illustrates a method for manufacturing a semiconductor device with a two-layer wiring structure, when forming a multilayer wiring structure with three or more layers, the above steps can be repeated to form each layer. That is, by repeatedly performing the steps for forming the interlayer insulating layer 4 and the steps for forming the surface protective layer 8, a multilayer pattern can be formed. Moreover, in the above example, the photosensitive resin composition of this embodiment can form not only the surface protective layer 8 but also the interlayer insulating layer 4.

[0165] [Electronic Components]

[0166] Next, the electronic component of this embodiment will be described. The electronic component of this embodiment has a patterned, cured film formed by the above-described manufacturing method, serving as an interlayer insulating layer or a surface protective layer. The electronic component includes semiconductor devices, multilayer wiring boards, and various electronic devices. Specifically, the patterned, cured film can be used as a surface protective layer for semiconductor devices, an interlayer insulating layer, an interlayer insulating layer for multilayer wiring boards, etc. The electronic component of this embodiment is not particularly limited in that it has a surface protective layer or an interlayer insulating layer film formed using the above-described photosensitive resin composition, and various structures can be adopted.

[0167] Furthermore, the aforementioned photosensitive resin composition also exhibits excellent stress relief and adhesion properties, and therefore can be used as a structural material in various encapsulation components with various structures developed in recent years. Figure 6 and Figure 7 A cross-sectional structure of an example of such a semiconductor device is shown.

[0168] Figure 6 This is a schematic cross-sectional view showing the wiring structure as one embodiment of a semiconductor device. Figure 6 The semiconductor device 600 shown includes: a silicon wafer 23; an interlayer insulating layer 11 disposed on one side of the silicon wafer 23; an Al wiring layer 12 disposed on the interlayer insulating layer 11, including a pad 15 and having a pattern; an insulating layer 13 (e.g., a P-SiN layer) and a surface protective layer 14, having an opening formed in the pad 15, and being sequentially stacked on the interlayer insulating layer 11 and the Al wiring layer 12; an island-shaped core 18 disposed on the surface protective layer 14 near the opening; and a rewiring layer 16 that is connected to the pad 15 within the opening of the insulating layer 13 and the surface protective layer 14, and extends on the surface protective layer 14 in such a way that it is connected to the side opposite to the core 18 and the surface protective layer 14. Additionally, the semiconductor device 600 includes: a cover layer 19 formed to cover the surface protective layer 14, the core 18, and the redistribution layer 16, with an opening formed in the redistribution layer 16 portion on the core 18; a conductive ball 17, which sandwiches a blocking metal 20 in the opening of the cover layer 19 and is connected to the redistribution layer 16; a protruding edge 21 for holding the conductive ball; and a bottom filler 22 disposed on the cover layer 19 surrounding the conductive ball 17. The conductive ball 17 serves as an external connection terminal and is formed of solder, gold, etc. The bottom filler 22 is provided to relieve stress during the mounting of the semiconductor device 600.

[0169] Figure 7 This is a schematic cross-sectional view showing the wiring structure as one embodiment of a semiconductor device. Figure 7In the semiconductor device 700, an Al wiring layer (not shown) and a pad 15 of the Al wiring layer are formed on a silicon wafer 23. An insulating layer 13 is formed on top of the pad 15, and a surface protective layer 14 of the device is further formed thereon. A rewiring layer 16 is formed on the pad 15, and the rewiring layer 16 extends to the upper part of the connection portion 24 with the conductive ball 17. In addition, a cover layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 via a barrier metal 20.

[0170] exist Figure 6 , Figure 7 In semiconductor devices, the aforementioned photosensitive resin composition can be used not only as a material for forming the interlayer insulating layer 11 and the surface protective layer 14, but also as a material for forming the capping layer 19, the core 18, the protrusion 21, the bottom filler 22, etc. The cured body using the aforementioned photosensitive resin composition exhibits excellent adhesion to metal layers such as the Al wiring layer 12 and the rewiring layer 16, as well as sealing materials, and also has a high stress relief effect. Therefore, semiconductor devices using this cured body for the capping layer 19, the core 18, the solder protrusion 21, the bottom filler 22 used in flip chips, etc., become devices with extremely high reliability.

[0171] The photosensitive resin composition of this embodiment is particularly preferably used in... Figure 6 and Figure 7 Figure 6 Figure 7 The semiconductor device having a rewiring layer 16 includes a surface protective layer 14 and / or a capping layer 19. The thickness of the surface protective layer or capping layer can be, for example, 3–20 μm or 5–15 μm.

[0172] By using the photosensitive resin composition of this embodiment, curing can be performed at a low temperature of 200°C or below in the aforementioned heat treatment process, which conventionally requires temperatures of 300°C or higher. Furthermore, since the photosensitive resin composition of this embodiment exhibits less volume shrinkage (curing shrinkage) during heat treatment processes seen in photosensitive polyimides and the like, a decrease in dimensional accuracy can be prevented. The patterned cured film formed from the photosensitive resin composition of this embodiment has a high glass transition temperature, thus becoming a surface protective layer with excellent heat resistance. As a result, electronic components such as semiconductor devices with excellent reliability can be obtained with high yield and high production volume.

[0173] Example

[0174] The present invention will be further illustrated below with examples. However, the present invention is not limited to the following examples.

[0175] The following shows the materials used to prepare the photosensitive resin compositions of the examples and comparative examples.

[0176] ((A) Component: Alkali-soluble resin)

[0177] P-1 to P-9 were prepared as component (A). The Mw and Tg of P-1 to P-9 are summarized in Table 1.

[0178] (P-1) Cresol Phenolic Resin (m-cresol / p-cresol (molar ratio) = 60 / 40, Mw = 12000, Tg = 165℃, product name "EP4020G", manufactured by ASAHIYUKIZAICORPORATION)

[0179] (P-2) Cresol Phenolic Resin (m-cresol / p-cresol (molar ratio) = 60 / 40, Mw = 4500, Tg = 150℃, product name "EP4080G", manufactured by ASAHIYUKIZAICORPORATION)

[0180] (P-3)

[0181] In a flask, 35.6 g of 4-hydroxyphenyl methacrylate, 78.0 g of ethyl 2-hydroxymethacrylate, 20.0 g of N-acryloyloxyethyl hexahydrophthalimide (product name "M-140", manufactured by TOAGOSEICO.,LTD.), 300 g of N,N-dimethylacetamide (DMAC), and 6.43 g of azobisisobutyronitrile (AIBN) were added, and the mixture was reacted at 80 °C for 6 hours under a nitrogen atmosphere. After adding 200 g of methanol, the polymer precipitated was slowly added dropwise to 1000 g of deionized water, filtered, and dried to obtain P-3.

[0182] (P-4)

[0183] 44.5 g of 4-hydroxyphenyl methacrylate, 39.0 g of 2-hydroxymethacrylate, 45.0 g of N-acryloyloxyethyl hexahydrophthalimide, 300 g of DMAC, and 6.43 g of AIBN were added to a flask, and the mixture was reacted at 80 °C for 6 hours under a nitrogen atmosphere. After adding 200 g of methanol, the polymer precipitated was slowly added dropwise to 1000 g of deionized water, filtered, and dried to obtain P-4.

[0184] (P-5)

[0185] 43.0 g of methacrylic acid, 39.0 g of ethyl 2-hydroxymethacrylate, 20.0 g of N-acryloyloxyethyl hexahydrophthalimide, 300 g of DMAC, and 5.10 g of AIBN were added to a flask, and the mixture was reacted at 80 °C for 6 hours under a nitrogen atmosphere. After adding 200 g of methanol, the precipitated resin was slowly added dropwise to 1000 g of deionized water, filtered, and dried to obtain P-5.

[0186] (P-6)

[0187] In a 300 mL flask equipped with a stirrer, thermometer, nitrogen substitution device (nitrogen inlet tube), and reflux cooler with a moisture receiver, 14.64 g (0.04 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (product name "BIS-AP-AF", manufactured by Central Glass Co., Ltd.), 19.48 g (0.045 mol) of polyoxypropylene diamine (product name "D-400", manufactured by BASF), 2.485 g (0.01 mol) of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropylamine (product name "BY16-871EG", manufactured by Dow Corning Toray Co., Ltd.), and 80 g of N-methyl-2-pyrrolidone (NMP) as a solvent were added and stirred to dissolve the amine components in the solvent. The flask was cooled in an ice bath, and 31 g (0.1 mol) of 4,4'-oxophthalic dianhydride (ODPA) was gradually added to the solution inside the flask. After the addition was complete, nitrogen gas was blown in while the solution was heated to 180 °C and held at that temperature for 5 hours to obtain a P-6 NMP solution.

[0188] (P-7)

[0189] A flask equipped with a stirrer, thermometer, nitrogen substitution apparatus (nitrogen inlet tube), and a reflux cooler with a moisture receiver was filled with 7.15 g (0.025 mol) of 5,5'-methylenebis(benzoimide acid) (product name "MBAA", manufactured by WAKAYAMASEIKA CORPORATION, molecular weight 286), 25.98 g (0.06 mol) of "D-400 (polyoxypropylene diamine)", and 2.48 g (0.01 mol) of "BY16-871EG (3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropylamine)" as the diamine, and 110 g of NMP as the solvent. The mixture was stirred to dissolve the diamine components in the solvent. The flask was cooled in an ice bath, and 31 g (0.1 mol) of ODPA was gradually added to the solution in the flask in small amounts. After the addition was completed, nitrogen gas was blown in while the solution was heated to 180°C and kept at that temperature for 5 hours to obtain a P-7 NMP solution.

[0190] (P-8)

[0191] 44.5 g of 4-hydroxyphenyl methacrylate, 39.0 g of 2-hydroxymethacrylate, 45.0 g of methyl methacrylate, 300 g of DMAC, and 6.43 g of AIBN were added to a flask, and the mixture was reacted at 80 °C for 6 hours under a nitrogen atmosphere. After adding 200 g of methanol, the polymer precipitated was slowly added dropwise to 1000 g of deionized water, filtered, and dried to obtain P-8.

[0192] (P-9)

[0193] In a 100 mL three-necked flask equipped with a stirrer, nitrogen inlet tube, and thermometer, 55 g of ethyl lactate was weighed, and the following polymer monomers were added: 34.7 g of n-butyl acrylate (BA), 2.2 g of lauryl acrylate (LA), 3.9 g of acrylic acid (AA), 2.6 g of hydroxybutyl acrylate (HBA), 1.7 g of 1,2,2,6,6-pentamethylpiperidin-4-ylmethacrylic acid (product name "FA-711MM", manufactured by Hitachi Chemical Co., Ltd.), and 0.29 g of AIBN. The mixture was stirred at room temperature (25 °C) at approximately 160 rpm (min). -1 The mixture was stirred at a controlled speed, and nitrogen gas was introduced at a flow rate of 400 mL / min for 30 minutes to remove dissolved oxygen. Afterward, the nitrogen flow was stopped, the flask was sealed, and the temperature was raised to 65°C in a constant-temperature water bath over approximately 25 minutes. This temperature was maintained for 10 hours to allow the polymerization reaction to proceed, yielding an ethyl lactate solution of acrylate resin P-9. The polymerization rate at this point was 99%.

[0194] [Table 1]

[0195]

[0196] ((B) Component: Thermosetting resin)

[0197] (B-1): 4,4',4”-Ethylenetri[2,6-(methoxymethyl)phenol] (Product name "HMOM-TPHAP", manufactured by Honshu Chemical Industry Co., Ltd.)

[0198] (B-2): Bisphenol A bis(triethylene glycol glycidyl ether) ether (product name "BEO-60E", manufactured by New Japan Chemical Co., Ltd.)

[0199] ((C) Ingredient: Photosensitizer)

[0200] (C-1): 1-Naphthoquinone-2-diazido-5-sulfonate of tris(4-hydroxyphenyl)methane (esterification rate approximately 95%)

[0201] ((D) Component: Low molecular weight compound with phenolic hydroxyl groups)

[0202] (D-1): 1,1-Bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane (product name "TrsP-PA-MF", manufactured by Honshu Chemical Industry Co., Ltd.)

[0203] A photosensitive resin composition was prepared by mixing components (A) to (D) in the proportions (parts by mass) shown in Table 2, 120 parts by mass of ethyl lactate as a solvent, and 2 parts by mass of a 50% ethanol solution of 3-epoxypropoxypropyltriethoxysilane (product name "KBE-403", manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent. The mixture was then pressure filtered using a polytetrafluoroethylene resin filter with 3 μm pores.

[0204] [Table 2]

[0205]

[0206] <Evaluation of Photosensitive Resin Compositions>

[0207] The photosensitive resin compositions were evaluated as shown below. The results are presented in Table 3.

[0208] (Preparation of evaluation samples)

[0209] A photosensitive resin composition was applied to a 6-inch silicon wafer with copper sputtered onto its surface using a spin coater to achieve a cured film thickness of 10 μm. The resin film was then formed by heating at 100°C for 5 minutes on a hot plate. A photomask designed to obtain a 10 mm wide stripe pattern was then used in a high-precision parallel exposure machine (product name "EXM-1172-B-∞", manufactured by ORCMANUFACTURING CO.,LTD.) at 1000 mJ / cm². 2 The resin film was exposed under certain conditions and developed using a 2.38% by mass TMAH aqueous solution, thereby obtaining a strip pattern of the resin film. After heating the strip pattern under nitrogen at 200°C for 2 hours, it was immersed in a copper etching solution to produce a strip sample of a cured film with a thickness of 10 μm and a width of 10 mm.

[0210] (Resistant to fatigue damage)

[0211] Fatigue tests were conducted on the above-mentioned long strip samples under the following conditions using a tensile testing machine (AG-1kNXplus) with a special thermostatic bath manufactured by Shimadzu Corporation.

[0212] Condition (1): Under the conditions of setting the temperature to 25℃, the distance between the clamps to 20mm, the test speed to 5mm / min, and the stress of the repeated load to 100MPa, the long strip sample is repeatedly stretched (0~100MPa).

[0213] Condition (2): Under the conditions of setting the temperature to -55℃, the distance between the clamps to 20mm, the test speed to 5mm / min, and the stress of the repeated load to 120MPa, the long strip sample is repeatedly stretched (0~120MPa).

[0214] The fatigue resistance was evaluated by conducting three measurements under various conditions. The case where the average number of tensile cycles that caused the long strip sample to break was more than 1,000 cycles, which was designated as "A", the case where the average number of cycles was 100 to 1,000 cycles, which was designated as "B", and the case where the fracture occurred in less than 100 cycles, which was designated as "C".

[0215] (elongation)

[0216] In the embodiment, for the long strip sample that had undergone 100 cycles of fatigue testing under the above conditions, a tensile testing instrument (AG-1kNXplus) with a special constant temperature bath manufactured by Shimadzu Corporation was used to stretch the sample under the conditions of a set temperature of 25°C, a distance between the clamps of 20 mm, and a test speed of 5 mm / min, and the elongation at fracture was measured.

[0217] (Yield stress)

[0218] In the tensile test described above, the stress at the intersection of the tangent line in the graph representing 5% elongation and the tangent line in the graph representing 15% elongation, obtained by plotting the elongation rate on the horizontal axis and the stress on the vertical axis, is defined as the yield stress.

[0219] (Young's modulus)

[0220] In the above tensile test, the Young's modulus was calculated from the slope of the curve obtained by plotting the elongation rate on the horizontal axis and the stress on the vertical axis within the elongation range of 0 to 5%.

[0221] The strip sample prepared in the comparative example fractured after less than 100 cycles in the fatigue test. Therefore, the elongation, yield stress and Young's modulus of the comparative example were measured using a strip sample that had not undergone fatigue testing.

[0222] (Glass transition temperature)

[0223] The viscoelasticity of the strip sample was measured using a dynamic viscoelasticity measuring device manufactured by UBM, under the conditions of a distance of 20 mm between the clamps, a frequency of 10 Hz, a heating rate of 5 °C / min, and a temperature range of 40–260 °C. The temperature representing the maximum value of tanδ was taken as the glass transition temperature (Tg).

[0224] (Adhesion rate)

[0225] A photosensitive resin composition was applied to the surface of an electrolytically plated copper substrate using a spin coater to achieve a cured film thickness of 10 μm. The resin film was then formed by heating at 120°C for 3 minutes on a hot plate. Next, the resin film was cured by heating at 200°C for 2 hours under a nitrogen atmosphere to produce a sample for evaluating adhesion.

[0226] For samples used to evaluate adhesion rate, a temperature cycling test was repeatedly performed 200 times under atmospheric pressure, air atmosphere, temperature range of -65 to 150°C, and stop time of 15 minutes, with the starting and ending temperatures varying from -65°C. The samples were then cut into a grid shape using the transverse cutting method specified in JIS K 5600-5-6. Next, adhesive tape with an adhesion strength of 10 ± 1 N per 25 mm width was applied to a 25-mass lattice (cured film). Within 5 minutes of application, the tape was peeled off vertically in 0.5 to 1.0 seconds. The number of lattices peeled off along the cut edge or at the intersection was measured to calculate the proportion (adhesion rate) of lattices (cured film) adhered to the electroplated copper substrate. The adhesion rate was evaluated as follows: 100% adhesion rate was designated as "A", 75% or higher but less than 100% as "B", and less than 75% as "C".

[0227] (reliability)

[0228] On an 8-inch silicon wafer with a thickness of 400 μm, a photosensitive resin composition was spin-coated to a cured film thickness of 10 μm. The first cured film was then formed by heating at 100°C for 5 minutes on a hot plate, followed by heating at 200°C for 2 hours under nitrogen atmosphere. A seed layer was formed by sputtering a 200 nm Cu layer onto a 50 nm Ti layer, and the resist material was patterned. Electrolytic plating was then performed to deposit a copper layer with a thickness of 5 μm. The resist material was stripped by NMP, and Cu and Ti were removed by etching to create a first copper pattern with a diameter of 350 μm. For areas outside the copper pattern, a photomask was designed with a copper mesh pattern and a copper residue ratio of 70%.

[0229] Next, a photosensitive resin composition was applied to the copper using a spin coater to achieve a cured film thickness of 5 μm. After heating at 100°C for 5 minutes on a hot plate, a photomask designed to form an 80 μm diameter opening in the center of the first copper pattern with a diameter of 350 μm was used. The mixture was then subjected to 600 mJ / cm² exposure using a stepper exposure machine (CERMAPRECISION, INC. Sc6k). 2 After exposure, development was performed using a 2.38% by mass TMAH aqueous solution to create an 80 μm diameter layer. A second cured film was then fabricated by heating at 200°C for 2 hours under nitrogen atmosphere.

[0230] A seed layer of 200 nm Cu was formed on 50 nm Ti using a sputtering apparatus. A resist material was patterned using a photomask designed to create a 240 μm diameter opening in the center of a first copper pattern with a diameter of 350 μm. Electrolytic plating was then used to deposit copper to a thickness of 5 μm. The resist material was then stripped using NMP, and Cu and Ti were removed by etching to create a second copper pattern with a diameter of 240 μm. For areas outside the copper pattern, a photomask was used with a copper mesh pattern and a 30% copper residue ratio. Flux was applied to a second copper pattern with a diameter of 240 μm, and a solder ball (manufactured by SENJUMETAL INDUSTRY CO.,LTD., ECOSOLDERBALL SM705) with a diameter of 250 μm was mounted. After reflowing under nitrogen atmosphere and contour conditions based on JEDEC (Semiconductor Technology Association; J-STD-020D), the flux was cleaned to obtain a package for reliability evaluation.

[0231] The above-mentioned package was subjected to temperature cycling tests under the JESD22-A104conditionB specification, with 1000 cycles of 15 minutes at -55°C and 15 minutes at 125°C. 300 locations on the sidewalls of the 240μm diameter second-layer copper pattern were observed. Cases with less than 5% crack occurrence were designated as "A", 5-20% as "B", and more than 20% as "C". The package reliability (thermal shock reliability) was then evaluated.

[0232] [Table 3]

[0233]

[0234] As shown in Table 3, it can be confirmed that the fatigue test under conditions (1) and (2) is related to the reliability of the package. By evaluating the fatigue resistance of the cured film, the thermal shock reliability (package reliability) that requires time during sample preparation and evaluation can be easily evaluated in a short time. When using a photosensitive resin composition with fatigue resistance of more than 100 cycles sorted in the fatigue test, a patterned cured film with excellent thermal shock reliability (package reliability) can be formed, and the semiconductor device using the patterned cured film also has excellent thermal shock reliability.

[0235] Symbol Explanation

[0236] 1-Semiconductor substrate, 2-Protective film, 3-First conductor layer, 4-Interlayer insulating layer, 5-Photosensitive resin layer, 6A, 6B, 6C-Window portion, 7-Second conductor layer, 8-Surface protective layer, 11-Interlayer insulating layer, 12-Al wiring layer, 13-Insulating layer, 14-Surface protective layer, 15-Pad portion, 16-Rewiring layer, 17-Conductive ball, 18-Core portion, 19-Cover layer, 20-Barrier metal, 21-Protruding edge, 22-Bottom filler, 23-Silicon chip, 24-Connector portion, 100, 200, 300, 400-Structure, 500-Semiconductor device, 600-Semiconductor device, 700-Semiconductor device.

Claims

1. A method for sorting a photosensitive resin composition, wherein, With 100–2000 mJ / cm 2 A strip sample of a cured film with a thickness of 10 μm and a width of 10 mm was prepared by exposing the resin film of the photosensitive resin composition to nitrogen and then heat-treating it at 150–250 °C for 1–3 hours. Fatigue tests were conducted on the long strip sample under the following conditions: a set temperature of 25℃, a clamping distance of 20mm, a test speed of 5mm / min, and a repeated load stress of 100MPa. The photosensitive resin composition was selected from those subjected to more than 100 cycles of tensile testing until the strip sample broke.

2. The sorting method for the photosensitive resin composition according to claim 1, wherein, Under the conditions of a set temperature of 25°C, a clamping distance of 20 mm, and a test speed of 5 mm / min, the elongation at break of the long strip sample after 100 cycles of the fatigue test was 10-60%.

3. The sorting method for the photosensitive resin composition according to claim 2, wherein, The yield stress of the long strip sample in the tensile test is 120-200 MPa.

4. The sorting method for the photosensitive resin composition according to claim 2 or 3, wherein, The Young's modulus of the long strip sample in the tensile test is 0.5 to 2.8 GPa.

5. The sorting method for the photosensitive resin composition according to any one of claims 1 to 4, wherein, The glass transition temperature of the cured film is above 150°C.

6. A method for sorting a photosensitive resin composition, wherein, With 100–2000 mJ / cm 2 A strip sample of a cured film with a thickness of 10 μm and a width of 10 mm was prepared by exposing the resin film of the photosensitive resin composition to nitrogen and then heat-treating it at 150–250 °C for 1–3 hours. Fatigue tests were conducted on the long strip sample under the following conditions: a set temperature of -55℃, a clamping distance of 20mm, a test speed of 5mm / min, and a repeated load stress of 120MPa. The photosensitive resin composition was selected from those subjected to more than 100 cycles of tensile testing until the strip sample broke.

7. The sorting method for the photosensitive resin composition according to claim 6, wherein, Under the conditions of a set temperature of 25°C, a clamping distance of 20 mm, and a test speed of 5 mm / min, the elongation at break of the long strip sample after 100 cycles of the fatigue test was 10-60%.

8. The sorting method for the photosensitive resin composition according to claim 7, wherein, The yield stress of the long strip sample in the tensile test is 120-200 MPa.

9. The sorting method for the photosensitive resin composition according to claim 7 or 8, wherein, The Young's modulus of the long strip sample in the tensile test is 0.5 to 2.8 GPa.

10. The sorting method of the photosensitive resin composition according to any one of claims 7 to 9, wherein, The glass transition temperature of the cured film is above 150°C.

11. A photosensitive resin composition comprising: (A) Components: Alkali-soluble resin; (B) Composition: Thermosetting resin; (C) Ingredients: Photosensitizer; and (D) Components: Low-molecular-weight compounds with phenolic hydroxyl groups. in, Component (A): The alkali-soluble resin is a compound having phenolic hydroxyl or carboxyl groups, and the alkali-soluble resin having imide groups in component (A) is used in combination with phenolic resin. With 100–2000 mJ / cm 2 A resin film of a photosensitive resin composition is exposed to nitrogen and heat-treated at 150–250°C for 1–3 hours to produce a strip sample of cured film with a thickness of 10 μm and a width of 10 mm. Under the conditions of a set temperature of 25°C, a clamping distance of 20 mm, a test speed of 5 mm / min, and a stress of 100 MPa for repeated loading, a fatigue test is performed on the strip sample by repeated tensile stress, and the number of tensile cycles until the strip sample breaks is more than 100.

12. A photosensitive resin composition comprising: (A) Components: Alkali-soluble resin; (B) Composition: Thermosetting resin; (C) Ingredients: Photosensitizer; and (D) Components: Low-molecular-weight compounds with phenolic hydroxyl groups. in, Component (A): The alkali-soluble resin is a compound having phenolic hydroxyl or carboxyl groups, and the alkali-soluble resin having imide groups in component (A) is used in combination with phenolic resin. With 100–2000 mJ / cm 2 A resin film of a photosensitive resin composition is exposed to nitrogen and heat-treated at 150–250°C for 1–3 hours to produce a strip sample of cured film with a thickness of 10 μm and a width of 10 mm. Under the conditions of a set temperature of -55°C, a clamping distance of 20 mm, a test speed of 5 mm / min, and a stress of 120 MPa for repeated loading, a fatigue test is performed on the strip sample by repeated tensile stress, and the number of tensile cycles until the strip sample breaks is more than 100.

13. A method for manufacturing a patterned curable film, comprising: The process of coating a portion or the entire surface of a substrate with a photosensitive resin composition sorted using the sorting method of any one of claims 1 to 10 and drying it to form a resin film. A process of exposing at least a portion of the resin film; The process of developing the exposed resin film to form a patterned resin film; and The process of heating the patterned resin film.

14. A method for manufacturing a semiconductor device, wherein, The patterned curing film formed by the method for manufacturing the patterned curing film according to claim 13 serves as an interlayer insulating layer or a surface protective layer.

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