JP2019109295A - Photosensitive resin composition and electronic device - Google Patents

Abstract

To provide a photosensitive resin composition having excellent insulation reliability.SOLUTION: There is provided a photosensitive resin composition for an insulating material comprising a thermosetting resin, a curing agent and a photoacid generator, which comprises a heat base generator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition and an electronic device.

  Until now, various developments have been made in photosensitive resin compositions. As this type of technology, for example, the technology described in Patent Document 1 is known. Patent Document 1 describes the use of a photoacid generator in a photosensitive resin composition for the purpose of improving photocuring (Patent Document 1 Claim 1).

JP, 2017-141356, A

  However, as a result of the present inventor's examination, in the photosensitive resin composition of the said patent document 1, it turned out that there is room for improvement in the point of insulation reliability.

The inventors further studied and found that the use of an acid quencher in the photosensitive resin film disposed between the Cu wires can enhance the insulation reliability between the Cu wires. Although the detailed mechanism is not clear, the acid quencher can trap the acid generated from the photoacid generator in the photosensitive resin film, so that the elution of Cu from the Cu wiring by the acid can be suppressed. Can be considered to be
Based on such findings, further intensive studies have shown that the insulation reliability as an insulation material is improved by employing a thermal base generator as an acid quencher in a photosensitive resin composition containing a photoacid generator. It has been found that it is possible to complete the present invention.

According to the invention
What is claimed is: 1. A photosensitive resin composition for an insulating material, comprising a thermosetting resin, a curing agent, and a photoacid generator,
A photosensitive resin composition is provided, which comprises a thermal base generator.

  Moreover, according to this invention, the electronic device provided with the hardened | cured material of the said photosensitive resin composition is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in insulation reliability and an electronic device using the same are provided.

It is a sectional view showing the composition of the electronic device concerning this embodiment.

Hereinafter, the outline | summary of the photosensitive resin composition which concerns on embodiment of this invention is demonstrated.
The photosensitive resin composition of the present embodiment can include a thermosetting resin, a curing agent, a photoacid generator, and a thermal base generator. Such a photosensitive resin composition can be used as an insulating material.

  According to the findings of the present inventor, when a photosensitive resin film made of a photosensitive resin composition containing a thermal base generator is used as an insulating layer covering a Cu wiring pattern (Cu circuit), Cu under high temperature and humidity conditions is used. It has been found that the occurrence of conduction (shorting) between wires can be suppressed.

The detailed mechanism is not clear, but it is guessed as follows.
In conventional photosensitive resin compositions, since the photoacid generator generates an acid upon exposure, the acidity (pH) in the photosensitive resin film is increased, whereby Cu constituting the Cu wiring is formed. Etc., and metal migration will cause conduction.
On the other hand, by using the thermal base generator in combination with the photoacid generator, the acid generated from the photoacid generator by exposure can be trapped by the base generated from the thermal base generator by heat treatment. Since the rise of the acidity in the photosensitive resin film (cured film) after the heat treatment can be suppressed, it is considered that the above-mentioned metal elution can be suppressed and the insulation reliability between the metal circuits can be improved.

  According to the photosensitive resin composition of the present embodiment, a negative photosensitive resin composition can be obtained, and a cured film excellent in connection reliability can be realized. The cured film of such a photosensitive resin composition can be suitably used for various electronic devices. Therefore, in the electronic device provided with the cured product of the photosensitive resin composition of the present embodiment, improvement in production stability and reliability is expected.

  Hereinafter, each component of the photosensitive resin composition of this embodiment is explained in full detail.

<Thermosetting resin>
The photosensitive resin composition of the present embodiment can contain an epoxy resin.

  The epoxy resin can include a multifunctional epoxy resin having two or more epoxy groups in the molecule. Thereby, the film physical property and processability in the resin film of the photosensitive resin composition can be enhanced.

  Examples of the polyfunctional epoxy resin include phenol novolac epoxy resin, cresol novolac epoxy resin, cresol naphthol epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, phenoxy resin, naphthalene skeleton epoxy resin, bisphenol A Epoxy resin, bisphenol A diglycidyl ether epoxy resin, bisphenol F epoxy resin, bisphenol F diglycidyl ether epoxy resin, bisphenol S diglycidyl ether epoxy resin, glycidyl ether epoxy resin, cresol novolac epoxy resin, aroma Aliphatic epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, polyfunctional alicyclic epoxy resin And the like. These may be used alone or in combination of two or more. Among these, a phenol novolac epoxy resin can be used from the viewpoint of easy availability.

  The said photosensitive resin composition can contain the solid epoxy resin which has a 2 or more epoxy group in a molecule | numerator as polyfunctional epoxy resin. As said solid epoxy resin, it has a 2 or more epoxy group and can use what is solid at room temperature 25 degreeC. Thereby, the film physical property and processability in the resin film of the photosensitive resin composition can be enhanced.

  The said photosensitive resin composition can contain the liquid epoxy resin which has a 2 or more epoxy group in a molecule | numerator as polyfunctional epoxy resin. The said liquid epoxy resin can function as a film forming agent, and can improve the brittleness of the cured film of the photosensitive resin composition.

  As the liquid epoxy resin, an epoxy compound which has two or more epoxy groups and is liquid at room temperature of 25 ° C. can be used. The viscosity at 25 ° C. of this liquid epoxy resin is, for example, 1 mPa · s to 8000 mPa · s, preferably 5 mPa · s to 1500 mPa · s, and more preferably 10 mPa · s to 1400 mPa · s. .

  The liquid epoxy resin may include, for example, one or more selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, alkyl diglycidyl ether and alicyclic epoxy. These may be used alone or in combination of two or more. Among these, alkyl diglycidyl ether can be used from the viewpoint of reducing cracks after development.

  The epoxy equivalent of the liquid epoxy resin is, for example, 100 g / eq or more and 200 g / eq or less, preferably 105 g / eq or more and 180 g / eq or less, and more preferably 110 g / eq or more and 170 g / eq or less. . Thereby, the brittleness of a cured film can be improved.

  The lower limit of the content of the liquid epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, with respect to the whole nonvolatile components of the photosensitive resin composition. It is. Thereby, the brittleness of the finally obtained cured film can be improved. On the other hand, the upper limit of the content of the liquid epoxy resin is, for example, 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass, with respect to the whole nonvolatile components of the photosensitive resin composition. It is below. Thereby, balance of the film | membrane characteristic of a cured film can be aimed at.

  The lower limit value of the total content of the solid epoxy resin and the liquid epoxy resin is, for example, 40% by mass or more, preferably 45% by mass or more, with respect to the whole nonvolatile components of the photosensitive resin composition. Is 50% by mass or more. Thereby, the heat resistance and mechanical strength of the cured film finally obtained can be improved. On the other hand, the upper limit value of the total content of the solid epoxy resin and the liquid epoxy resin is, for example, 80% by mass or less, preferably 75% by mass or less, based on the whole nonvolatile components of the photosensitive resin composition. Preferably it is 70 mass% or less. Thereby, the patterning property can be improved.

  In the present embodiment, the whole non-volatile component of the photosensitive resin composition refers to the non-volatile component in the photosensitive resin composition, and refers to the remainder excluding volatile components such as water and solvent.

  As thermosetting resins other than the epoxy resin mentioned above, for example, polyimide resin, bismaleimide resin, urea (urea) resin, melamine resin, polyurethane resin, cyanate ester resin, silicone resin, oxetane resin (oxetane compound), Examples include (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, benzoxazine resins and the like.

<Hardening agent>
The photosensitive resin composition of the present embodiment can contain a curing agent. Thereby, the film physical property and processability in the resin film of the photosensitive resin composition can be enhanced. The curing agent is not particularly limited as long as it accelerates the polymerization / crosslinking reaction of the above-mentioned thermosetting resin (epoxy resin).

  The above-mentioned curing agent can include a curing agent having a phenolic hydroxyl group, and specifically, it is preferable to include a polyfunctional phenol resin having two or more phenolic hydroxyl groups in the molecule. Thereby, it is thought that thermal expansion of a cured film can be made still smaller and it can contribute to the reliability improvement of an electronic device. As a polyfunctional phenol resin, although it can select suitably from well-known things, a novolak type phenol resin, a resol type phenol resin, a trisphenyl methane type phenol resin, an aryl alkylene type phenol resin can be used, for example. From the viewpoint of good development characteristics, novolac phenolic resins can be used. The weight average molecular weight of the phenol resin is preferably 200 to 20,000, more preferably 300 to 15,000, and still more preferably 350 to 13,000 (hereinafter, “〜” is an upper limit value unless otherwise specified. And including the lower limit).

  The content of the curing agent is, for example, 10 to 60% by mass, preferably 20 to 50% by mass, and more preferably 20 to 45% by mass, with respect to the entire nonvolatile components of the photosensitive resin composition. By setting it as this range, the heat resistance and intensity | strength of hardened | cured material improve.

<Photo acid generator>
The photosensitive resin composition of the present embodiment can contain a photoacid generator. Thereby, the processability at the time of patterning, such as sensitivity and resolution, can be improved.
As said photo-acid generator, the photo-acid generator which generate | occur | produces an acid by irradiation of active rays, such as an ultraviolet-ray, is contained. Examples of the photoacid generator include onium salt compounds, for example, iodonium salts such as diazonium salts and diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, triarylbirylium salts, benzylpyridinium thiocyanate, dialkylphenacyl Mention may be made of cationic photopolymerization initiators such as sulfonium salts and dialkyl hydroxyphenyl phosphonium salts. Moreover, a photosensitive diazoquinone compound can also be mentioned. The photosensitive diazoquinone compound is preferably used particularly when the photosensitive resin composition is made positive. In addition, as a photo-acid generator, since a photosensitive composition contacts metal, what has no generation | occurence | production of the hydrogen fluoride by decomposition | disassembly like a methide salt type and a borate salt type is preferable.

  The lower limit value of the content of the photoacid generator is, for example, 0.3% by mass or more, preferably 0.5% by mass or more, with respect to the whole nonvolatile components of the photosensitive resin composition, and more preferably Is 0.7% by mass or more. Thereby, in the photosensitive resin composition, the patterning property can be improved. On the other hand, the upper limit value of the content of the photoacid generator is, for example, 5% by mass or less, preferably 4.5% by mass or less, with respect to the whole nonvolatile components of the photosensitive resin composition. Preferably it is 4 mass% or less. Thereby, the long-term storage property before hardening of the photosensitive resin composition can be improved.

<Thermal base generator>
As the above-mentioned thermal base generator, one capable of generating a base by heat treatment can be used. The heat treatment may be, for example, an exposure post-treatment, and specific examples thereof include post-exposure heat treatment and curing treatment.

  As the above-mentioned thermal base generator, it is possible to use one which absorbs at the exposure wavelength, that is, one which has a relatively low degree of photodegradation. That is, the thermal base generator is different from the photobase generator with a relatively high degree of photodegradation at the exposure wavelength from the viewpoint of optical characteristics. As such a thermal base generator, for example, when the exposure wavelength is (365 nm (i line)), those having no aromatic fused ring such as anthracene, naphthalene and derivatives thereof can be used. . Thereby, at the time of exposure processing, generation of a base from the thermal base generator can be suppressed, and therefore, it is possible to prevent deterioration of the patterning property of the photoacid generator due to the acid.

  The thermal base generator may be either an ionic thermal base generator or a nonionic thermal base generator, but from the viewpoint of reliability, it is preferable to use an ionic thermal base generator. The ionic thermal base generator is easily decomposed by heat treatment as compared to the nonionic thermal base generator, and accordingly, the base is easily generated, so that it is considered that the insulation reliability can be improved.

  The base generated from the thermal base generator can include a base having a nitrogen atom. A base having a nitrogen atom is excellent in acid trapping ability. For this reason, it is possible to improve insulation reliability. Also, crosslinking of the epoxy resin or phenol resin can be promoted by the base.

  The melting point of the thermal base generator is, for example, 50 ° C. or more and 200 ° C. or less, preferably 55 ° C. or more and 180 ° C. or less, and more preferably 60 ° C. or more and 150 ° C. or less. By providing the melting point equal to or lower than the heating temperature in the above heat treatment, the thermal decomposability can be enhanced, so that the insulation reliability due to the generated base can be improved.

The content of the thermal base generator is, for example, 1 wt% or more and 100 wt% or less with respect to 100 wt% of the photoacid generator. By setting the above lower limit value or more, the insulation reliability can be improved. By setting the lower limit value or less, the patterning property can be improved.
Further, from the viewpoint of achieving both insulation reliability and patterning properties, the content of the non-ionic base generator is preferably 1 wt% or more and 20 wt% or less, more preferably 10 wt% or more and 15 wt% or less based on the photoacid generator. The content of the ionic base generator is preferably 1 wt% to 10 wt%, more preferably 2 wt% to 5 wt%, based on 100 wt% of the photoacid generator.

<Surfactant>
The photosensitive resin composition of the present embodiment can contain a surfactant. By including the surfactant, the wettability at the time of coating can be improved, and a uniform resin film and a cured film can be obtained. In addition, it can be expected to prevent residue and pattern floating during development. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic-based surfactants.

  The surfactant preferably includes a surfactant containing at least one of a fluorine atom and a silicon atom. In addition to the ability to obtain a uniform resin film (improvement of coatability) and the improvement of developability, this also contributes to the improvement of adhesive strength. As such surfactant, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom is preferable. As a commercial item which can be used as surfactant, for example, F-251, F-253, F-281, F-430, F-477, F-551, and the “Megafuck” series manufactured by DIC Corporation. F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F- 565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc. Fluorine-containing surfactants having oligomer structure, Ftergent 250 manufactured by Neos Co., Ltd., fluorine-containing nonionic surfactants such as Ftergent 251, etc., SILFOAM (registered trademark) series manufactured by Wacker Chemie (eg SD 100 TS, SD 670, SD 850, SD 860, SD 882), and other silicone surfactants.

  The photosensitive resin composition of the present embodiment can contain other additives, as needed, in addition to the components described above. Examples of other additives include antioxidants, fillers such as silica, sensitizers, film-forming agents, adhesion assistants, and the like.

<Adhesive aid>
The photosensitive resin composition of the present embodiment can contain a cohesion aid. Thereby, the adhesiveness of a cured film can be improved further.

The adhesion assistant is not particularly limited, and for example, silane coupling agents such as aminosilane, epoxysilane, acrylsilane, mercaptosilane, vinylsilane, ureidosilane, or sulfide silane can be used. One type of silane coupling agent may be used alone, or two or more types may be used in combination. Among these, it is more preferable to use epoxysilane (that is, a compound containing both an epoxy site and a group capable of generating a silanol group by hydrolysis) in one molecule.
As an aminosilane, for example, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyl Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N -Β (aminoethyl) γ-aminopropylmethyldiethoxysilane, or N-phenyl-γ-amino-propyltrimethoxysilane, etc. may be mentioned. As epoxysilane, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane Etc. Examples of acrylic silanes include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane. Examples of mercaptosilanes include 3-mercaptopropyltrimethoxysilane. Examples of the vinylsilane include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane. As ureido silane, 3-ureido propyl triethoxysilane etc. are mentioned, for example. Examples of sulfide silanes include bis (3- (triethoxysilyl) propyl) disulfide or bis (3- (triethoxysilyl) propyl) tetrasulfide.

  The content of the adhesion promoter can be, for example, preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass, based on the total amount of non-volatile components of the photosensitive resin composition.

  The photosensitive resin composition of the present embodiment may be varnish-like or film-like.

  The preparation method of the photosensitive resin composition of this embodiment is not specifically limited, It can manufacture by a generally well-known method. For example, a varnish-like photosensitive resin composition (resin varnish) is obtained by blending the components (raw materials) described above and a solvent and mixing them uniformly.

<Solvent>
The photosensitive resin composition of the present embodiment can contain a solvent. An organic solvent can be included as a solvent.
The organic solvent can be used without particular limitation as long as it can dissolve each component of the photosensitive resin composition and does not react chemically with each component. For example, acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene Examples thereof include glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone. These can be suitably selected by the desired film thickness. These may be used alone or in combination of two or more.

  It is preferable that the said solvent is used so that the density | concentration of the non-volatile component whole quantity in the photosensitive resin composition may be 30-75 mass%, for example. By setting this range, each component can be sufficiently dissolved, and good coating properties can be ensured.

  On the other hand, the film-like photosensitive resin composition (photosensitive resin film) is, for example, applied to a coating film (resin film) obtained by applying a varnish-like photosensitive resin composition on a carrier substrate, It can be obtained by performing a solvent removal treatment. The solvent content of the photosensitive resin film can be 10% by weight or less with respect to the entire photosensitive resin composition. For example, the solvent removal treatment can be performed under the conditions of 80 ° C. to 150 ° C. and 1 minute to 30 minutes. This makes it possible to remove the solvent sufficiently while suppressing the progress of curing of the photosensitive resin composition.

  In the step of forming the resin film of the photosensitive resin composition on the carrier substrate, for example, the photosensitive resin composition is dissolved and dispersed in a solvent or the like to prepare a resin varnish, and the resin is prepared using various coaters. After applying a varnish to a carrier base material, the method of drying this, the method of spray-coating a resin varnish on a carrier base material using a spray apparatus, and the like, and the like can be mentioned. Among these, a method of applying a resin varnish to a carrier substrate using various coaters such as a spin coater, a comma coater, a die coater and the like and then drying the same is preferable. Thereby, the photosensitive resin film with a carrier base material which does not have a void and has uniform thickness can be manufactured efficiently.

  The photosensitive resin film with a carrier substrate may be in the form of a roll that can be wound up, or may be in the form of a rectangular sheet. The surface of the photosensitive resin film with a carrier substrate may be, for example, exposed or may be covered with a protective film (cover film). Although a film having a known protective function can be used as the protective film, for example, a PET film may be used.

  Further, in the present embodiment, for example, a polymer film or a metal foil can be used as the carrier base material. The polymer film is not particularly limited, but, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as polycarbonate and silicone sheet, heat resistance such as fluorine resin and polyimide resin The thermoplastic resin sheet etc. which have are mentioned. The metal foil is not particularly limited, and, for example, copper and / or copper based alloy, aluminum and / or aluminum based alloy, iron and / or iron based alloy, silver and / or silver based alloy, gold and gold based alloy And zinc and zinc based alloys, nickel and nickel based alloys, tin and tin based alloys, and the like. Among these, a sheet composed of polyethylene terephthalate is most preferable because of its low cost and easy control of peel strength. Thereby, it becomes easy to peel a carrier base material with moderate intensity from a photosensitive resin film with a carrier base material.

  The film thickness of the said photosensitive resin film can be designed according to the film thickness of the final cured film. The lower limit of the film thickness of the photosensitive resin film is, for example, 40 μm or more, preferably 50 μm or more, and more preferably 60 μm or more. Thereby, a thick photosensitive resin film can be realized. The embeddability of an electronic member such as a semiconductor chip of a photosensitive resin film can be enhanced. Moreover, the mechanical strength of the photosensitive resin film can be improved. On the other hand, the upper limit of the film thickness of the photosensitive resin film is not particularly limited, but may be, for example, 300 μm or less, 250 μm or less, or 200 μm or less. Thereby, thinning of the electronic device provided with the cured film of the photosensitive resin film can be realized.

Hardened film, method of forming it
The method for obtaining the cured film of the photosensitive resin composition of the present embodiment is not particularly limited. For example, the following steps:
A step of providing a photosensitive resin composition on a substrate (step 1),
A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin film (step 2),
Exposing the photosensitive resin film to actinic radiation (step 3);
Developing the exposed photosensitive resin film to obtain a patterned resin film (step 4);
Heating the patterned resin film to obtain a cured film (step 5);
Thus, a cured film of the photosensitive resin composition of the present embodiment can be obtained.

  In the step 1, the substrate is not particularly limited, and examples thereof include a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer and the like. The substrate includes, in addition to the unprocessed substrate, for example, a substrate on which a semiconductor element or a display element is formed. Moreover, a printed wiring board etc. may be sufficient. The substrate surface may be treated with an adhesion promoter such as a silane coupling agent in order to improve adhesion. The photosensitive resin composition can be provided on the substrate by spin coating, spray coating, immersion, printing, roll coating, an inkjet method, or the like.

  In the step 2, the temperature of the heating and drying is usually 80 to 140 ° C, preferably 90 to 120 ° C. The heating and drying time is usually 30 to 600 seconds, preferably about 30 to 300 seconds. A photosensitive resin film is formed by removing the solvent by this heating and drying. Heating is typically performed with a hot plate, an oven or the like. The thickness of the photosensitive resin film is preferably, for example, about 1 to 500 μm.

In the step 3, for example, X-rays, electron beams, ultraviolet rays, visible light and the like can be used as actinic rays for exposure. In terms of wavelength, actinic radiation of 200 to 500 nm is preferred. The light source is preferably a mercury lamp g-line, h-line or i-line in view of pattern resolution and handleability. Also, two or more light beams may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable.
After exposure, the photosensitive resin film is heated again (heating after exposure). The temperature and time of post-exposure heating are, for example, about 80 to 140 ° C. and about 10 to 300 seconds.

  In step 4, development can be performed using a suitable developer, for example, using a method such as immersion, paddle, rotary spray, and the like. Thereby, a patterned resin film can be obtained.

  The developer that can be used is not particularly limited, but in the present embodiment, a developer mainly composed of an organic solvent (a developer in which 95% by mass or more of the component is an organic solvent) is preferable. Specific examples thereof include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. Further, as a developer, an organic solvent developer composed of only an organic solvent may be used.

  After the development step, the developer may not be washed with the rinse solution, but if necessary, the developer may be removed by washing with the rinse solution. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether and the like. You may use these individually or in combination of 2 or more types.

  In step 5, a cured film can be obtained by heating the patterned resin film. In this embodiment, 150-300 degreeC is preferable and, as for this heating temperature, 170-200 degreeC is more preferable. By setting this temperature range, it is possible to achieve both the rate of the crosslinking reaction and the uniform curing of the entire film. The heating time is not particularly limited but is, for example, in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature rising oven capable of setting a temperature program, or the like. As atmosphere gas at the time of performing heat processing, it may be air or inert gas, such as nitrogen and argon. Moreover, you may heat under pressure reduction.

The photosensitive resin composition of the present embodiment is used in applications of insulating materials such as permanent films, protective films, insulating films and rewiring materials in electric and electronic devices (electronic devices).
In the electronic device provided with the cured product of the photosensitive resin composition of the present embodiment, improvement in production stability and reliability is expected.
Here, "electrical / electronic equipment" refers to semiconductor chips, semiconductor elements, printed wiring boards, electric circuits, display devices such as television receivers and monitors, information communication terminals, light emitting diodes, physical batteries, chemical batteries, etc. Elements, devices, final products, and other general equipment related to electricity that apply engineering technology.

A penetration electrode substrate is mentioned as one of the examples of the use of the photosensitive resin composition of this embodiment. Hereinafter, an electronic device provided with the through electrode substrate will be described with reference to FIG.
FIG. 1A is a cross-sectional view showing the configuration of the electronic device of the present embodiment. FIG. 1 (b) is an enlarged view of a part of the electronic device shown in FIG. 1 (a).

As shown in FIG. 1A, the electronic device 100 according to this embodiment includes the through electrode substrate 200. The through electrode substrate 200 includes an organic insulating layer (photosensitive resin layer 220), a plurality of through electrodes (vias 242) penetrating the upper surface to the lower surface of the organic insulating layer, and a semiconductor chip 210 embedded in the organic insulating layer. And a lower wiring layer 252 provided on the lower surface of the organic insulating layer, and an upper wiring layer 250 provided on the upper surface of the organic insulating layer.
The photosensitive resin layer 220 and the upper wiring layer 250 can be formed of a cured film (cured product) of the photosensitive resin composition of the present embodiment. For the formation of the photosensitive resin layer 220, a film-like photosensitive resin composition can be used. In addition, a varnish-like (liquid at room temperature) photosensitive resin composition can be used to form the upper wiring layer 250.

  The electronic device 100 according to the present embodiment does not use a thick film package substrate having a core layer or a buildup layer, and a package structure such as a package on package is formed by the through electrode substrate 200 described above. Therefore, in the electronic device 100, the overall height of the package structure can be reduced.

  Further, as shown in FIG. 1A, the electronic device 100 of the present embodiment can have a package on package structure in which the semiconductor package 300 is mounted on the through electrode substrate 200. For example, the electronic device 100 according to this embodiment can further include the semiconductor package 300 having a known package structure mounted on the upper wiring layer 250 of the through electrode substrate 200. Thereby, multifunctionalization of the electronic device 100 can be realized. In addition, the mounting density of the electronic device 100 can be increased.

  In the present embodiment, for example, as shown in FIG. 1A, in the semiconductor package 300, the semiconductor chip 310 is mounted on the substrate 320, and the substrate 320 and the semiconductor chip 310 are bonded via the bonding wire 330. May have the following structure. In the semiconductor package 300, a plurality of semiconductor chips 310 may be provided, and a plurality of semiconductor chips 310 may be arranged in the planar direction or the stacking direction. The semiconductor chip 310 and the bonding wire 330 may be sealed by a sealing material layer 340. The sealing material layer 340 can be formed, for example, by curing a known sealing resin composition. In addition, solder bumps 360 may be formed on the substrate 320 of the semiconductor package 300 as external terminals. The semiconductor package 300 can be bump-connected to the through electrode substrate 200 through the solder bumps 360.

  In addition, the electronic device 100 according to this embodiment can include the solder bumps 260 provided on the lower surface of the lower wiring layer 252 of the through electrode substrate 200. As a result, the solder bumps 260 function as external terminals, thereby enabling external connection with other electronic components.

  As such an electronic device 100, for example, the lower wiring layer 252 of the through electrode substrate 200 can further include a motherboard bump-connected through the solder bumps 260. Thereby, the mechanical strength of the electronic device 100 can be increased, and further multifunctionalization can be realized. At this time, in the through electrode substrate 200, the side surfaces and the upper and lower surfaces thereof may be sealed together with the semiconductor package 300 by a sealing material layer formed by curing a known sealing resin composition. Thereby, connection reliability and mechanical strength of the electronic device 100 can be improved.

  The through electrode substrate 200 included in the electronic device 100 according to the present embodiment includes an organic wiring layer 250 and a lower wiring layer 252 formed on the upper surface and the lower surface of the organic insulating layer (photosensitive resin layer 220), respectively. The semiconductor chip 210 in the insulating layer has a structure in which the through electrode (via 242) electrically connecting the wiring layers is embedded therein, so it exhibits excellent mechanical strength as compared with a structure without these. be able to.

  In the embodiment, the organic insulating layer in the through electrode substrate 200 can be formed of a cured product of the photosensitive resin composition described above. Thus, since the method of opening by the photoresist method can be employed, the diameter of the opening, in other words, the diameter of the via 242 can be further reduced compared to the method of opening by laser irradiation. The integration density of the semiconductor chip 210 and the via 242 can be increased in the plane of the through electrode substrate 200. In addition, the mechanical strength of the through electrode substrate 200 can be enhanced by curing the photosensitive resin composition.

  In addition, the lower limit of the film thickness of the organic insulating layer (photosensitive resin layer 220) in the through electrode substrate 200 of the present embodiment may be, for example, 40 μm or more, more preferably 50 μm or more, and still more preferably It may be 60 μm or more. Thereby, the mechanical strength of penetration electrode substrate 200 can be improved. In addition, the embeddability of the semiconductor chip 210 can be improved. On the other hand, the upper limit of the thickness of the organic insulating layer may be, for example, 300 μm or less, more preferably 250 μm or less, and still more preferably 200 μm or less. Thereby, the height of the electronic device 100 can be reduced.

  The through electrode (via 242) is, for example, a conductive frustum made of one or more metals selected from the group consisting of copper, gold, silver, nickel, etc. Specifically, a conductive frustum It may be a body, a conductive polygonal frustum, or more specifically a copper truncated cone (copper pillar).

  In the electronic device 100 according to the present embodiment, as shown in FIG. 1A, the wires forming the lower wiring layer 252 may be formed to the outside of the semiconductor chip 210 in a cross sectional view. As a result, the inter-electrode pitch width of the structure in which the plurality of semiconductor chips 210 are mounted at high density can be expanded to the optimal pitch width for connection to the solder bumps 260. That is, the mounting density of the semiconductor chip 210 can be increased.

  Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than the above can also be adopted.

<Preparation of Photosensitive Resin Composition>
The raw material of each component blended according to Table 1 was dissolved in PGMEA to obtain a mixed solution. Thereafter, the mixed solution was filtered through a 0.2 μm polypropylene filter to obtain a photosensitive resin composition having a solid content of 50% by mass.
The detail of the raw material of each component in Table 1 is as follows.

(Thermosetting resin)
Epoxy resin 1: Multifunctional epoxy resin represented by the following structure (solid epoxy resin at room temperature 25 ° C., EPPN 201 manufactured by Nippon Kayaku Co., Ltd., phenol novolac epoxy resin)

  Epoxy resin 2: bisphenol F diglycidyl ether represented by the following structure (liquid epoxy resin at room temperature 25 ° C., DIC Corporation, EXA-830 CRP, epoxy equivalent 155-163 g / eq, viscosity (25 ° C.): 1100 to 1500 mPa・ S)

(Hardening agent)
Phenolic resin 1: Novolak type phenolic resin represented by the following structure (PR 51470, manufactured by Sumitomo Bakelite Co., Ltd.)

(Photo acid generator)
Photoacid generator 1: Triarylsulfonium salt (San-Apro Co., CPI-310B)

(Thermal base generator)
Thermal base generator 1: 2-Nitrophenyl methyl 4-methacryloylpyridine 1-carboxylate represented by the following formula (WPBG-165, manufactured by Wako Pure Chemical Industries, molecular weight: 348.36, melting point: 55 ° C., powder)

Thermal base generator 2: 1,2-Diisopropyl-3- [Bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (WPBG-266, Wako Pure Chemical Industries, Ltd., molecular weight: 495.67, melting point: 115 ° C, powder)

Thermal base generator 3: 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate represented by the following formula (WPBG-300, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: 621.75, melting point: 115 ° C, powder)

(Photo base generator)
Photobase generator 1: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate (WPBG-140, manufactured by Wako Pure Chemical Industries, molecular weight: 346.34, melting point: 124 ° C.) represented by the following formula

Photobase generator 2: 9-Anthrylmethyl N, N-diethylcarbamate (WPBG-018, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: 307.39, melting point: 72 to 74 ° C.) represented by the following formula

(Adhesive aid)
Adhesion assistant 1: Epoxy group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-403E)
(Surfactant)
Surfactant 1: Fluorine-based surfactant (Megaphorc R-41 manufactured by DIC Corporation, fluorine-containing / lipophilic group-containing oligomer, 20% by mass solution of propylene glycol monomethyl ether acetate)

  The obtained photosensitive resin composition was evaluated based on the following evaluation items. The evaluation results are shown in Table 1.

(reliability)
Cu was plated on a base material (heat-resistant vinyl chloride resin sheet) with a width of 30 μm / pitch of 20 μm and a height of 10 to 15 μm to prepare a Cu wiring board in which a comb-shaped Cu wiring was formed.
The obtained photosensitive resin composition was applied onto a Cu wiring substrate by spin coating so as to have a thickness of 30 μm after drying, and dried at 100 ° C. for 3 minutes to form a photosensitive resin film.
The obtained photosensitive resin film was exposed on the entire surface of the i-line having an exposure wavelength of 365 nm under the condition of 400 mJ / cm ² using an automatic exposure machine.
Subsequently, the Cu wiring substrate was heated after exposure with a hot plate at 70 ° C. for 5 minutes.
Subsequently, the Cu wiring substrate was immersed in PGMEA (propylene glycol monomethyl ether acetate) for 20 seconds.
Subsequently, the photosensitive resin film was cured under nitrogen at 170 ° C. for 120 minutes.
Thereafter, the end (Cu electrode) of the Cu wiring of the Cu wiring substrate was soldered to the electrode wiring, and this electrode wiring was connected to the B-HAST apparatus.
<Insulation reliability test>
A bias of 130 ° C / 85%, 3.5 V is applied to the B-HAST device connected with the Cu wiring board, and the insulation resistance value between the Cu wiring of the Cu wiring board is automatically measured at intervals of 6 minutes, and from the start of the test The time to leak (h) was measured. Here, when the measured insulation resistance value was 1.0 × 10 ⁴ Ω or less, it was determined that the dielectric breakdown (leakage to the Cu wiring) occurred.
The results of the above insulation reliability test were evaluated based on the following criteria.
<Standard>
○: time from start of test to leak 210 hours or more Δ: time from start of test to leak 100 hours or more and less than 210 hours ×: time from start of test to leak less than 100 hours

(Patternability)
Photosensitive resin composition A obtained in each of the examples and comparative examples, and a photosensitive resin composition similar to the photosensitive resin composition A except that it does not contain the thermal base generator or photo base generator described in Table 1 Each of the resin compositions B was applied onto a substrate by spin coating to a dry thickness of 10 μm and dried at 100 ° C. for 3 minutes to form a photosensitive resin film.
With respect to the obtained photosensitive resin film, an i-line having an exposure wavelength of 365 nm was entirely exposed at a predetermined exposure amount using an automatic exposure machine.
Subsequently, the substrate was heated after exposure with a hot plate at 70 ° C. for 5 minutes, and then the substrate was developed with PGMEA for 20 seconds by a spray developing machine.
The conditions of the predetermined exposure amount were changed, and the maximum exposure amount (mJ / cm ² ) was measured when the photosensitive resin film was completely dissolved in the above-mentioned development processing.
About the result of said maximum exposure amount, the photosensitive resin composition A and the photosensitive resin composition B corresponding to it were compared, and it evaluated based on the following references | standards.
<Standard>
○: When the maximum exposure of the photosensitive resin composition A is the same as the maximum exposure of the photosensitive resin composition B containing no thermal base generator Δ: The maximum exposure of the photosensitive resin composition A is thermal Based on the maximum exposure equivalent to the photosensitive resin composition B not containing a base generator, lower than 200 mJ / cm ² : the maximum exposure of the photosensitive resin composition A does not contain a thermal base generator In the case of higher than 200 mJ / cm ^{2 based} on the maximum exposure equivalent to the photosensitive resin composition B

  It turned out that the photosensitive resin composition of Examples 1-9 can implement | achieve the photosensitive resin composition film excellent in reliability compared with Comparative Examples 1-3. Moreover, it turned out that the photosensitive resin composition of Examples 1-9 can implement | achieve the photosensitive resin composition film excellent in patterning property compared with Comparative Examples 2 and 3.

100 electronic device 200 through electrode substrate 210 semiconductor chip 220 photosensitive resin layer 242 via 250 upper wiring layer 252 lower wiring layer 260 solder bump 300 semiconductor package 310 semiconductor chip 320 substrate 330 bonding wire 340 sealing material layer 360 solder bump

Claims (14)

What is claimed is: 1. A photosensitive resin composition for an insulating material, comprising a thermosetting resin, a curing agent, and a photoacid generator,
Photosensitive resin composition containing a heat base generator. The photosensitive resin composition according to claim 1, wherein
The photosensitive resin composition whose content of the said heat | fever base generation agent is 1 wt% or more and 100 wt% or less with respect to 100 wt% of said photo-acid generators. It is the photosensitive resin composition of Claim 1 or 2, Comprising:
The photosensitive resin composition in which the base generated from the said thermal base generator contains the base which has a nitrogen atom. The photosensitive resin composition according to any one of claims 1 to 3, wherein
The photosensitive resin composition in which the said heat | fever base generator contains an ionic-type heat base generator. It is the photosensitive resin composition of any one of Claim 1 to 4, Comprising:
The photosensitive resin composition whose melting | fusing point of the said thermal base generator is 50 to 200 degreeC. The photosensitive resin composition according to any one of claims 1 to 5, wherein
The photosensitive resin composition in which the said thermosetting resin contains the solid epoxy resin which has a 2 or more epoxy group in a molecule | numerator. The photosensitive resin composition according to any one of claims 1 to 6, wherein
The photosensitive resin composition in which the said thermosetting resin contains the liquid epoxy resin which has a 2 or more epoxy group in a molecule | numerator. It is the photosensitive resin composition according to claim 7, which is
The photosensitive resin composition whose content of the said liquid epoxy resin is 5 mass% or more and 40 mass% or less with respect to the whole non-volatile component of the said photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 8, wherein
The photosensitive resin composition in which the said hardening agent contains a phenol type hardening agent. It is the photosensitive resin composition according to claim 9,
The photosensitive resin composition in which the said phenol-type hardening | curing agent contains the polyfunctional phenol resin which has a 2 or more phenolic hydroxyl group in a molecule | numerator. The photosensitive resin composition according to any one of claims 1 to 10, wherein
Photosensitive resin composition containing surfactant. The photosensitive resin composition according to any one of claims 1 to 11, wherein
Photosensitive resin composition containing a silane coupling agent. The photosensitive resin composition according to any one of claims 1 to 12, wherein
A varnish-like or film-like photosensitive resin composition.   An electronic device comprising the cured product of the photosensitive resin composition according to any one of claims 1 to 13.

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