JP2021047378A - Photosensitive resin composition, method for manufacturing electronic device and electronic device - Google Patents

Abstract

To provide a photosensitive resin composition that can give a cured film having sufficient heat resistance even when a heating temperature in a curing process is low, and that can suppress shrinkage of a film in a curing process.SOLUTION: The photosensitive resin composition comprises an epoxy resin (A1) including a biphenyl skeleton and a glycidyl oxybenzene skeleton, and is a chemically amplified type. The glycidyl oxybenzene skeleton preferably comprises a diglycidyl oxybenzene skeleton.SELECTED DRAWING: Figure 1

Description

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

In the electrical and electronic fields, a photosensitive resin composition containing an epoxy resin may be used to form a cured film such as an insulating layer. Therefore, a photosensitive resin composition containing an epoxy resin has been studied so far.

As an example, Patent Document 1 describes a photosensitive resin composition containing an alkaline aqueous solution-soluble resin, a cross-linking agent, a photopolymerization initiator, and an epoxy resin represented by a specific general formula. Patent Document 1 describes that the photosensitivity of this photosensitive resin composition is good. Further, Patent Document 1 describes that the film formed by this photosensitive resin composition is excellent in flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance and the like. There is.

Japanese Unexamined Patent Publication No. 2016-80871

When forming a cured film in an electronic device using a photosensitive resin composition, a curing treatment by heat is usually performed. Specifically, first, a photosensitive resin composition is applied onto a substrate to form a film, and the film is patterned by exposure or development. Then, the patterned film is heat-treated to form a cured film.
In the formation of the cured film by heating as described above, it is preferable that the shrinkage of the film due to heating is suppressed. If the film shrinks significantly, problems such as impaired flatness of the film may occur.

As another viewpoint, in recent electronic device manufacturing, when the heating temperature during the curing process is required to be relatively low (for example, about 170 ° C.) due to the miniaturization and complexity of the element structure. There is.
However, if the heating temperature during the curing process is low, the curing reaction may not proceed sufficiently. As a result, a cured film having sufficient heat resistance may not be obtained. This is a problem in terms of the reliability of electronic devices.
Further, in the manufacture of electronic devices, heating such as reflow may be performed a plurality of times, and in this respect as well, improvement in heat resistance of the cured film is required.

The present invention has been made in view of these circumstances. An object of the present invention is a photosensitive resin composition capable of obtaining a cured film having sufficient heat resistance even at a low heating temperature during the curing treatment and suppressing shrinkage of the film during the curing treatment. To provide things.

The present inventors have completed the inventions provided below and solved the above problems.

According to the present invention
Provided is a photosensitive resin composition containing an epoxy resin (A1) containing a biphenyl skeleton and a glycidyloxybenzene skeleton, which is a chemically amplified type.

Further, according to the present invention.
A film forming step of forming a photosensitive resin film on a substrate using the above-mentioned photosensitive resin composition, and
The exposure step of exposing the photosensitive resin film and
A developing process for developing the exposed photosensitive resin film, and
A method for manufacturing an electronic device including the above is provided.

According to the present invention, a photosensitive resin composition capable of obtaining a cured film having sufficient heat resistance even at a low heating temperature during the curing treatment and suppressing shrinkage of the film during the curing treatment. Things are provided.

It is a vertical sectional view which shows an example of the structure of an electronic device. FIG. 2 is a partially enlarged view of the region surrounded by the chain line of FIG. It is a process drawing which shows the method of manufacturing the electronic device shown in FIG. It is a figure for demonstrating the method of manufacturing the electronic device shown in FIG. It is a figure for demonstrating the method of manufacturing the electronic device shown in FIG. It is a figure for demonstrating the method of manufacturing the electronic device shown in FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.
In order to avoid complication, (i) when there are a plurality of the same components in the same drawing, only one of them is coded and all of them are not coded, or (ii) especially in the figure. In 2 and later, the same components as in FIG. 1 may not be re-signed.
All drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawing do not necessarily correspond to the actual article.

In the present specification, the notation "XY" in the description of the numerical range means X or more and Y or less unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term "electronic device" as used herein refers to an element to which electronic engineering technology is applied, such as a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit display device, an information communication terminal, a light emitting diode, a physical battery, and a chemical battery. , Devices, final products, etc.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains an epoxy resin (A1) containing a biphenyl skeleton and a glycidyloxybenzene skeleton, and is a chemically amplified type.

In the field of photosensitive resin compositions, the term "chemically amplified" means that the active chemical species generated by irradiating the photosensitive resin composition with light are chained / catalytically. By inducing a chemical reaction, it means that the solubility of the composition in the developing solution changes and / or the curing reaction of the composition proceeds.
In particular, in the photosensitive resin composition of the present embodiment containing an epoxy resin, the active chemical species generated by light irradiation acts as a catalyst for the polymerization reaction of the epoxy group, so that the solubility change / curing reaction in the developing solution is caused. Occur.
Some of the known epoxy resin-containing photosensitive resin compositions are not of the chemically amplified type but are cured by a non-chemically amplified type, that is, a stoichiometric reaction of an epoxy resin-curing agent. The photosensitive resin composition of the present embodiment is different from such a composition.

As a reminder, the photosensitive resin composition of this embodiment is usually a negative type. That is, when the photosensitive resin composition of the present embodiment is exposed as a film, the high-exposure region in the film becomes insoluble in the developer, and the low-exposure region in the film dissolves in the developer. The negative type photosensitive resin composition may be advantageous for forming a pattern having a specific shape as compared with the positive type photosensitive resin composition.

Since the photosensitive resin composition of the present embodiment is a chemically amplified type, it is typically cured when irradiated with light. Therefore, a pattern can be formed on the substrate by selectively exposing the film formed on the substrate using the photosensitive resin composition of the present embodiment via a photomask.
By forming a cured film using the photosensitive resin composition of the present embodiment, shrinkage of the film during the curing process can be suppressed. As a guess, the polymer obtained by the epoxy resin-curing agent reaction tends to cure and shrink due to the formation of many three-dimensional network structures, but the epoxy resin polymerization reaction is two-dimensional ( Since many (linear) polymer structures are formed, it is presumed that shrinkage is relatively suppressed.
Further, since the photosensitive resin composition of the present embodiment is a chemically amplified type, the curing reaction proceeds catalytically, so it is presumed that the photosensitive resin composition is more easily cured at a relatively low temperature than the non-chemically amplified type. Will be done.

The epoxy resin (A1) contains a biphenyl skeleton and a glycidyloxybenzene skeleton. Since the skeleton contained in the epoxy resin (A1) is rigid, it is considered that the glass transition temperature of the final cured film can be increased. A high glass transition temperature leads to good heat resistance of the cured film. Incidentally, as "heat resistance", specifically, even if an electronic device is placed under high temperature and / or high humidity, dielectric breakdown of the cured film is unlikely to occur.

From the above merits, the photosensitive resin composition of the present embodiment is preferably used for forming an insulating layer in the rewiring layer in an electronic device.

The description of the photosensitive resin composition of the present embodiment will be continued.

(Epoxy resin (A1))
The photosensitive resin composition of the present embodiment contains an epoxy resin (A1) containing a biphenyl skeleton and a glycidyloxybenzene skeleton.

The biphenyl skeleton can have a structure in which some hydrogen atoms of _{biphenyl (C 6} H _5- C ₆ H _{5) are removed.}
The biphenyl skeleton may have a substituent other than a hydrogen atom. On the other hand, from the viewpoint of cost and the like, the biphenyl skeleton may be unsubstituted.

The glycidyloxybenzene skeleton can have a structure in which some hydrogen atoms of _{benzene (C 6} H _{6) are substituted with one or more glycidyloxy groups.}
The glycidyloxybenzene skeleton may have a substituent other than a hydrogen atom and a glycidyloxy group. On the other hand, from the viewpoint of cost and the like, the glycidyloxybenzene skeleton does not have to have a substituent other than a hydrogen atom and a glycidyloxy group.

From the viewpoint of increasing the glass transition temperature and particularly improving the heat resistance, the glycidyloxybenzene skeleton preferably contains at least a diglycidyloxybenzene skeleton (a benzene skeleton having two glycidyloxy groups).
The epoxy resin (A1) may contain both a monodiglycidyloxybenzene skeleton and a diglycidyloxybenzene skeleton, or may contain only one of them. From the viewpoint of synthesis / availability, the epoxy resin (A1) preferably contains both a monodiglycidyloxybenzene skeleton and a diglycidyloxybenzene skeleton.

More specifically, the epoxy resin (A1) contains a structural unit represented by the following general formula (1).

一般式（１）において、Ｒはグリシジルオキシ基であり、ｍは１〜３の整数である。ｍは好ましくは１または２である。
ｍが１の場合、エポキシ樹脂（Ａ１）は、ビフェニル骨格とモノグリシジルオキシベンゼン骨格を含む。
ｍが２の場合、エポキシ樹脂（Ａ１）は、ビフェニル骨格とジグリシジルオキシベンゼン骨格を含む。

In the general formula (1), R is a glycidyloxy group and m is an integer of 1 to 3. m is preferably 1 or 2.
When m is 1, the epoxy resin (A1) contains a biphenyl skeleton and a monoglycidyloxybenzene skeleton.
When m is 2, the epoxy resin (A1) contains a biphenyl skeleton and a diglycidyloxybenzene skeleton.

The photosensitive resin composition of the present embodiment may contain two or more epoxy resins (A1).
For example, in the photosensitive resin composition of the present embodiment, as the epoxy resin (A1), an epoxy resin containing a biphenyl skeleton and a monoglycidyloxybenzene skeleton and an epoxy resin containing a biphenyl skeleton and a diglycidyloxybenzene skeleton are used. It is preferable to contain it.
By using such a resin together, the balance of various performances can be improved.

The weight average molecular weight of the epoxy resin (A1) is not particularly limited, but is, for example, 100 to 50,000, preferably 500 to 10000. By adjusting the molecular weight of the epoxy resin (A1), the fluidity of the composition can be adjusted, and for example, improvement in flatness during spin coating can be expected.
The number average molecular weight can usually be determined as a standard polystyrene conversion value by gel permeation chromatography (GPC). When a commercially available product is used as the epoxy resin (A1), the catalog value may be referred to.

(Epoxy resin (A2))
The photosensitive resin composition of the present embodiment can contain an epoxy resin (A2) different from the epoxy resin (A1). As a result, it may be possible to reduce the cost of raw materials and improve the balance with effects other than heat resistance and suppression of film shrinkage.

As the epoxy resin (A2), for example, an epoxy resin having two or more epoxy groups in one molecule can be used. As the epoxy resin, monomers, oligomers, and polymers in general can be used. The molecular weight and molecular structure of the epoxy resin (A2) are not particularly limited.

Examples of the epoxy resin (A2) include phenol novolac type epoxy resin, cresol novolac type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenoxy resin, naphthalene skeleton type epoxy resin, and bisphenol A. Type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol F type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, cresol novolac type epoxy resin, fragrance Examples thereof include those that do not correspond to the epoxy resin (A1), such as group polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, and polyfunctional alicyclic epoxy resin.
The epoxy resin (A2) may be used alone or in combination of two or more.

When the epoxy resin (A2) is used, the epoxy resin (A2) is preferably a polyfunctional epoxy resin having trifunctionality or higher in the molecule (that is, a polyfunctional epoxy resin having three or more epoxy groups in one molecule). including. As a result, the film is sufficiently cured, and for example, the heat resistance and durability of the permanent film can be improved.
The upper limit of the number of functional groups of the polyfunctional epoxy resin is not particularly limited, but is, for example, 10 or less, preferably 7 or less, and more preferably 5 or less.

Examples of the trifunctional or higher functional epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, and tetramethylbisphenol F type. Epoxy resin and the like can be mentioned.

The epoxy resin (A2) may be solid or liquid at 25 ° C. (room temperature).
By using the solid epoxy resin (A2) at 25 ° C. (room temperature), it is easy to improve the mechanical properties of the final cured film.
By using the epoxy resin (A2) that is liquid at 25 ° C. (room temperature), for example, it is easy to improve the brittleness of the film. In addition, improvement in flatness during spin coating can be expected.

The weight average molecular weight of the epoxy resin (A2) is not particularly limited, but is, for example, 100 to 50,000, preferably 500 to 10000. By adjusting the molecular weight of the epoxy resin (A2), for example, the above-mentioned effect can be obtained more reliably.

(Amount of epoxy resin, ratio of (A1) and (A2), etc.)
The content of the epoxy resin in the photosensitive resin composition of the present embodiment is, for example, 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more in the non-volatile component. As a result, the heat resistance and mechanical strength of the finally obtained cured film can be sufficiently improved.
The content of the epoxy resin in the photosensitive resin composition of the present embodiment is, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less in the non-volatile components of the photosensitive resin composition. Is. Thereby, the patterning property can be improved.
In the above, the non-volatile component means the balance of the photosensitive resin composition excluding volatile components such as water and solvent. The content of the photosensitive resin composition with respect to the entire non-volatile component refers to the content of the photosensitive resin composition with respect to the entire non-volatile component excluding the solvent when the solvent is contained.
In the above, the "epoxy resin content" means the total amount of the epoxy resin (A1) and the epoxy resin (A2) when the photosensitive resin composition contains the epoxy resin (A2). When the photosensitive resin composition contains only the epoxy resin (A1), the content of the epoxy resin (A1) = the content of the epoxy resin.

When the photosensitive resin composition of the present embodiment contains the epoxy resin (A2), the amount thereof is preferably 0.1 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of the epoxy resin.
By using an appropriately large amount of the epoxy resin (A2), it is easy to sufficiently obtain the effect of the epoxy resin (A2). On the other hand, if the amount of the epoxy resin (A2) is not too large, a sufficient amount of the epoxy resin (A1) will be contained in the composition, and the effects such as heat resistance of the cured film and reduction of curing shrinkage will be further improved. Definitely easy to get.

(Phenoxy resin)
The photosensitive resin composition of the present embodiment preferably contains a phenoxy resin. Thereby, the flexibility of the cured film can be increased and the elongation can be improved.
The "phenoxy resin" is, in a narrow sense, a polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, but in the present specification, a high molecular weight obtained by a heavy addition reaction between a polyfunctional epoxy resin and polyfunctional phenols. Molecules (phenoxy resins in a broad sense) are also included in phenoxy resins.

The weight average molecular weight (Mw) of the phenoxy resin is not particularly limited, but is preferably 1000 to 100,000, more preferably 2000 to 80,000, for example. By using such a relatively high molecular weight phenoxy resin, it is possible to impart good flexibility to the resin film and impart sufficient solubility in a solvent.
The weight average molecular weight is measured, for example, as a polystyrene-equivalent value in a gel permeation chromatography (GPC) method.

The phenoxy resin may have a reactive group such as an epoxy group at both ends of the molecular chain or inside the molecular chain. The reactive group in the phenoxy resin is one capable of cross-linking with the epoxy group in the epoxy resin. By using such a phenoxy resin, the solvent resistance and heat resistance in the resin film can be enhanced.

As the phenoxy resin, one that is solid at 25 ° C. is preferably used. Specifically, a phenoxy resin having a non-volatile content of 90% by mass or more is preferably used. By using such a phenoxy resin, the mechanical properties of the cured product can be improved.

Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A type and bisphenol F type copolymerized phenoxy resin, biphenyl type phenoxy resin, bisphenol S type phenoxy resin, biphenyl type phenoxy resin and bisphenol. Examples thereof include a copolymerized phenoxy resin with an S-type phenoxy resin, and one or a mixture of two or more of these is used. Among these, a bisphenol A type phenoxy resin or a copolymerized phenoxy resin of a bisphenol A type and a bisphenol F type is preferably used.

When the photosensitive resin composition of the present embodiment contains a phenoxy resin, it can contain one or more phenoxy resins.
The lower limit of the phenoxy resin content is, for example, 3 parts by mass, preferably 5 parts by mass, and more preferably 7 parts by mass when the epoxy resin content (total of (A1) and (A2)) is 100 parts by mass. It is a department. This makes it possible to increase flexibility and elongation.
The upper limit of the phenoxy resin content is, for example, 30 parts by mass, preferably 20 parts by mass, and more preferably 15 parts by mass when the epoxy resin content (total of (A1) and (A2)) is 100 parts by mass. It is a department. As a result, it is possible to increase the solubility of the phenoxy resin and realize a photosensitive resin composition having excellent coatability.

(Photocationic polymerization initiator)
The photosensitive resin composition of the present embodiment contains a photocationic polymerization initiator. As a result, patterning performance such as sensitivity and resolution can be improved.
The photocationic polymerization initiator typically generates an active chemical species (cationic species) capable of polymerizing an epoxy group contained in an epoxy resin by irradiating with light such as g-ray or i-ray.

Examples of the photocationic polymerization initiator include onium salt compounds. More specifically, iodonium salts such as diazonium salt and diaryliodonium salt, sulfonium salt such as triarylsulfonium salt, triarylvirylium salt, benzylpyridinium thiocyanate, dialkylphenacil sulfonium salt, dialkylhydroxyphenylphosphonium salt and the like. Examples include photocationic polymerization initiators.
Above all, it is preferable to use a triarylsulfonium salt from the viewpoint of good patterning property.

Examples of the counter anion of the onium salt compound include borate anion, sulfonate anion, gallate anion, phosphorus anion, antimony anion and the like. More specifically, sulfonic acid anion, disulfonylimide acid anion, hexafluorophosphate anion, fluoroantimonate anion, tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion and the like can be mentioned.

When a photocationic polymerization initiator is used, it may be used alone or in combination of two or more.
When a photocationic polymerization initiator is used, the amount thereof is, for example, 0.3 to 10 parts by mass, preferably 0.% by mass, when the content of the epoxy resin (total of (A1) and (A2)) is 100 parts by mass. It is 5 to 8 parts by mass, more preferably 1 to 5 parts by mass. By setting the amount to 0.3 parts by mass or more, the patterning property can be improved. Further, by setting the amount to 10 parts by mass or less, the ionic component in the film can be reduced, and the insulating property and reliability of the cured film can be further improved.

(Adhesion aid)
The photosensitive resin composition of the present embodiment preferably contains an adhesion aid. Thereby, for example, the adhesion to the substrate can be further improved.

The adhesion aid is not particularly limited. For example, amino group-containing silane coupling agent, epoxy group-containing silane coupling agent, (meth) acryloyl group-containing silane coupling agent, mercapto group-containing silane coupling agent, vinyl group-containing silane coupling agent, ureido group-containing silane cup. A silane coupling agent such as a ring agent or a sulfide group-containing silane coupling agent can be used.
When a silane coupling agent is used, one type may be used alone, or two or more types may be used in combination.

Examples of the amino group-containing silane coupling agent include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyldiethoxy. Silane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-amino Examples thereof include propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-amino-propyltrimethoxysilane.
Examples of the epoxy group-containing silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidyl. Examples thereof include propyltrimethoxysilane.
Examples of the (meth) acryloyl group-containing silane coupling agent include γ-((meth) acryloyloxypropyl) trimethoxysilane, γ-((meth) acryloyloxypropyl) methyldimethoxysilane, and γ-((meth)). Acryloyloxypropyl) methyldiethoxysilane and the like.
Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane.
Examples of the vinyl group-containing silane coupling agent include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and the like.
Examples of the ureido group-containing silane coupling agent include 3-ureidopropyltriethoxysilane and the like.
Examples of the sulfide group-containing silane coupling agent include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.
Examples of the acid anhydride-containing silane coupling agent include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysisilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride and the like.

Examples of the adhesion aid include not only a silane coupling agent but also a titanium coupling agent, a zirconium coupling agent, and the like.

When the adhesion aid is used, it may be used alone or in combination of two or more kinds of adhesion aids.
When an adhesion aid is used, the amount used is preferably 0.3 to 15 parts by mass, more preferably 0, when the epoxy resin content (total of (A1) and (A2)) is 100 parts by mass. .4 to 12 parts by mass, more preferably 0.5 to 10 parts by mass.

(Surfactant)
The photosensitive resin composition of the present embodiment may contain a surfactant. By containing a surfactant, the wettability at the time of coating can be improved, and a uniform resin film and a cured film can be obtained. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, an alkyl-based surfactant, an acrylic-based surfactant, and the like.

The surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. As a result, a uniform resin film can be obtained (improvement of coatability), and in addition to improvement of developability, it also contributes to improvement of adhesive strength. As such a surfactant, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom is preferable. Commercially available products that can be used as surfactants include, for example, F-251, F-253, F-281, F-430, F-477, F-551, of the "Mega Fvck" series manufactured by DIC Co., Ltd. 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 oligomeric surfactants, Fluorine-containing nonionic surfactants such as Futtergent 250 and Futtergent 251 manufactured by Neos Co., Ltd., SILFOAM® series manufactured by Wacker Chemie (for example, SD 100 TS) , SD 670, SD 850, SD 860, SD 882) and other silicone-based surfactants.

When the photosensitive resin composition of the present embodiment contains a surfactant, it can contain one or more surfactants.
When the photosensitive resin composition of the present embodiment contains a surfactant, the amount thereof is, for example, 0.001 to 0.001 when the content of the epoxy resin (total of (A1) and (A2)) is 100 parts by mass. It is 1 part by mass, preferably 0.005 to 0.5 part by mass.

(solvent)
The photosensitive resin composition of the present embodiment preferably contains a solvent. As a result, a photosensitive resin film can be easily formed on the stepped substrate by the coating method. When the photosensitive resin composition of the present embodiment contains a solvent, the photosensitive resin composition of the present embodiment is, for example, varnish-like.
The solvent usually includes an organic solvent. The organic solvent is not particularly limited as long as each of the above-mentioned components can be dissolved or dispersed and does not substantially chemically react with each of the components.

Examples of the organic solvent include 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, and benzyl. Examples thereof include alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, diproprene glycol methyl-n-propyl ether, butyl acetate and γ-butyrolactone. These may be used alone or in combination of two or more.

When a solvent is used, the concentration of the non-volatile component in the photosensitive resin composition is preferably 30 to 75% by mass, more preferably 35 to 70% by mass. Within this range, each component can be sufficiently dissolved or dispersed. In addition, good coatability can be ensured, which in turn leads to improvement in flatness during spin coating. Further, by adjusting the content of the non-volatile component, the viscosity of the photosensitive resin composition can be appropriately controlled.

(Other ingredients)
The photosensitive resin composition of the present embodiment may contain components other than those listed above, if necessary, in addition to the above components. Examples of such components include antioxidants, fillers such as silica, sensitizers, filming agents and the like.

<Manufacturing method of electronic devices, electronic devices>
The method for manufacturing the electronic device of this embodiment is
A film forming step of forming a photosensitive resin film on a substrate using the above-mentioned photosensitive resin composition, and
The exposure process for exposing the photosensitive resin film and
The development process for developing the exposed photosensitive resin film and
including.
Further, the method for manufacturing an electronic device of the present embodiment preferably includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-mentioned developing step. As a result, a cured film having sufficient heat resistance can be obtained.
As described above, an electronic device including the cured film of the photosensitive resin composition of the present embodiment can be manufactured.

The method for manufacturing the electronic device of the present embodiment, the structure of the electronic device including the cured product of the photosensitive resin composition of the present embodiment, and the like will be described in more detail below with reference to the drawings.

FIG. 1 is a vertical cross-sectional view showing an example of the electronic device of the present embodiment. Further, FIG. 2 is a partially enlarged view of the region surrounded by the chain line of FIG.
In the following description, the upper side in FIG. 1 is referred to as "upper" and the lower side is referred to as "lower".

The electronic device 1 shown in FIG. 1 has a so-called package-on-package structure including a through electrode substrate 2 and a semiconductor package 3 mounted on the through electrode substrate 2.

The through electrode substrate 2 is provided on the insulating layer 21, a plurality of through wirings 221 penetrating from the upper surface to the lower surface of the insulating layer 21, the semiconductor chip 23 embedded inside the insulating layer 21, and the lower surface of the insulating layer 21. The lower layer wiring layer 24, the upper layer wiring layer 25 provided on the upper surface of the insulating layer 21, and the solder bumps 26 provided on the lower surface of the lower layer wiring layer 24 are provided.

The semiconductor package 3 includes a package substrate 31, a semiconductor chip 32 mounted on the package substrate 31, a bonding wire 33 that electrically connects the semiconductor chip 32 and the package substrate 31, and a semiconductor chip 32 and a bonding wire 33. It includes an embedded sealing layer 34 and solder bumps 35 provided on the lower surface of the package substrate 31.

Then, the semiconductor package 3 is laminated on the through electrode substrate 2. As a result, the solder bump 35 of the semiconductor package 3 and the upper wiring layer 25 of the through silicon via substrate 2 are electrically connected.

In such an electronic device 1, it is not necessary to use a thick substrate such as an organic substrate including a core layer in the through electrode substrate 2, so that the height can be easily reduced. Therefore, it is possible to contribute to the miniaturization of the electronic device incorporating the electronic device 1.

Further, since the through electrode substrate 2 having different semiconductor chips and the semiconductor package 3 are laminated, the mounting density per unit area can be increased. Therefore, it is possible to achieve both miniaturization and high performance.

Hereinafter, the through electrode substrate 2 and the semiconductor package 3 will be described in more detail.
The lower layer wiring layer 24 and the upper layer wiring layer 25 included in the through electrode substrate 2 shown in FIG. 2 include an insulating layer, a wiring layer, a through wiring, and the like, respectively. As a result, the lower layer wiring layer 24 and the upper layer wiring layer 25 include wiring inside or on the surface, and are electrically connected to each other via the through wiring 221 penetrating the insulating layer 21.

The wiring layer included in the lower wiring layer 24 is connected to the semiconductor chip 23 and the solder bump 26. Therefore, the lower wiring layer 24 functions as a rewiring layer of the semiconductor chip 23, and the solder bump 26 functions as an external terminal of the semiconductor chip 23.

As described above, the through wiring 221 shown in FIG. 2 is provided so as to penetrate the insulating layer 21. As a result, the lower layer wiring layer 24 and the upper layer wiring layer 25 are electrically connected, and the through silicon via substrate 2 and the semiconductor package 3 can be laminated, so that the functionality of the electronic device 1 can be improved. it can.

The wiring layer 253 included in the upper wiring layer 25 shown in FIG. 2 is connected to the through wiring 221 and the solder bump 35. Therefore, the upper wiring layer 25 is electrically connected to the semiconductor chip 23, functions as a rewiring layer of the semiconductor chip 23, and serves as an interposer interposed between the semiconductor chip 23 and the package substrate 31. Also works. The cured film of the photosensitive resin composition of the present embodiment can be used to form an insulating layer of the rewiring layer.

According to the present embodiment, the semiconductor chip 23 and the rewiring layer (upper layer wiring layer 25) provided on the surface of the semiconductor chip 23 are provided, and the insulating layer in the rewiring layer is the photosensitive layer of the present embodiment. It is possible to realize an electronic device composed of a cured product of a sex resin composition.

Since the through wiring 221 penetrates the insulating layer 21, the effect of reinforcing the insulating layer 21 can be obtained. Therefore, even when the mechanical strength of the lower layer wiring layer 24 and the upper layer wiring layer 25 is low, it is possible to avoid a decrease in the mechanical strength of the entire through electrode substrate 2. As a result, the lower layer wiring layer 24 and the upper layer wiring layer 25 can be further thinned, and the electronic device 1 can be further reduced in height.

In addition to the through wiring 221, the electronic device 1 shown in FIG. 1 also includes a through wiring 222 provided so as to penetrate the insulating layer 21 located on the upper surface of the semiconductor chip 23. As a result, the upper surface of the semiconductor chip 23 and the upper wiring layer 25 can be electrically connected to each other.

The insulating layer 21 is provided so as to cover the semiconductor chip 23. As a result, the effect of protecting the semiconductor chip 23 is enhanced. As a result, the reliability of the electronic device 1 can be improved. Further, an electronic device 1 that can be easily applied to a mounting method such as the package-on-package structure according to the present embodiment can be obtained.

The diameter W (see FIG. 2) of the through wiring 221 is not particularly limited, but is preferably about 1 to 100 μm, and more preferably about 2 to 80 μm. As a result, the conductivity of the through wiring 221 can be ensured without impairing the mechanical properties of the insulating layer 21.

The semiconductor package 3 shown in FIG. 1 may be a package of any form. For example, QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip Size Package), QFN (Quad Flat Non-Lead Page) Examples include LF-BGA (Lead Flame BGA) and the like.

The arrangement of the semiconductor chips 32 is not particularly limited, but as an example, in FIG. 1, a plurality of semiconductor chips 32 are laminated. As a result, the mounting density is increased. The plurality of semiconductor chips 32 may be arranged in the plane direction, or may be arranged in the plane direction while being laminated in the thickness direction.

The package substrate 31 may be any substrate, but is, for example, a substrate including an insulating layer, a wiring layer, a through wiring, and the like (not shown). Of these, the solder bump 35 and the bonding wire 33 can be electrically connected via the through wiring.

The sealing layer 34 is made of, for example, a known sealing resin material. By providing such a sealing layer 34, the semiconductor chip 32 and the bonding wire 33 can be protected from an external force and an external environment.

The semiconductor chip 23 included in the through electrode substrate 2 and the semiconductor chip 32 included in the semiconductor package 3 are arranged close to each other. As a result, it is possible to enjoy merits such as high speed and low loss of mutual communication. From this point of view, for example, of the semiconductor chip 23 and the semiconductor chip 32, one is used as an arithmetic element such as a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), or an AP (Application Processor), and the other is a DRAM (Dynamic Processor Access). If a storage element such as a Memory) or a flash memory is used, these elements can be arranged close to each other in the same device. As a result, it is possible to realize an electronic device 1 that has both high functionality and miniaturization.

Next, a method of manufacturing the electronic device 1 shown in FIG. 1 will be described.

FIG. 3 is a process diagram showing a method of manufacturing the electronic device 1 shown in FIG. 4 to 6 are diagrams for explaining a method of manufacturing the electronic device 1 shown in FIG. 1, respectively.

The method for manufacturing the electronic device 1 includes a chip arrangement step S1 for obtaining an insulating layer 21 so as to embed a semiconductor chip 23 and through silicon vias 221, 222 provided on the substrate 202, and an upper layer on the insulating layer 21 and the semiconductor chip 23. A through electrode substrate is formed by forming a solder bump 26, an upper layer wiring layer forming step S2 for forming the wiring layer 25, a substrate peeling step S3 for peeling the substrate 202, and a lower layer wiring layer forming step S4 for forming the lower layer wiring layer 24. It has a solder bump forming step S5 for obtaining 2 and a laminating step S6 for laminating the semiconductor package 3 on the through electrode substrate 2.

Among these, in the upper wiring layer forming step S2, the first resin obtained by arranging the photosensitive resin varnish 5 (crocodile-like photosensitive resin composition) on the insulating layer 21 and the semiconductor chip 23 to obtain the photosensitive resin layer 2510. The film arranging step S20, the first exposure step S21 for exposing the photosensitive resin layer 2510, the first developing step S22 for developing the photosensitive resin layer 2510, and the curing treatment for the photosensitive resin layer 2510. The first curing step S23, the wiring layer forming step S24 for forming the wiring layer 253, and the second resin for arranging the photosensitive resin varnish 5 on the photosensitive resin layer 2510 and the wiring layer 253 to obtain the photosensitive resin layer 2520. The film arranging step S25, the second exposure step S26 for exposing the photosensitive resin layer 2520, the second developing step S27 for developing the photosensitive resin layer 2520, and the curing treatment for the photosensitive resin layer 2520. The second curing step S28 and the through wiring forming step S29 for forming the through wiring 254 in the opening 424 (through hole) are included.

Hereinafter, each step will be described in sequence. The following manufacturing method is an example, and the present invention is not limited thereto.

[1] Chip placement step S1
First, as shown in FIG. 4A, a chip including a substrate 202, a semiconductor chip 23 and through wirings 221 and 222 provided on the substrate 202, and an insulating layer 21 provided so as to embed them. The embedded structure 27 is prepared.

The constituent material of the substrate 202 is not particularly limited, and examples thereof include a metal material, a glass material, a ceramic material, a semiconductor material, and an organic material. Further, as the substrate 202, a semiconductor wafer such as a silicon wafer, a glass wafer, or the like may be used.

The semiconductor chip 23 is adhered on the substrate 202. In this manufacturing method, as an example, a plurality of semiconductor chips 23 are placed side by side on the same substrate 202 while being separated from each other. The plurality of semiconductor chips 23 may be of the same type or different from each other. Further, the substrate 202 and the semiconductor chip 23 may be fixed via an adhesive layer (not shown) such as a die attach film.

If necessary, an interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23. The interposer functions as, for example, a rewiring layer of the semiconductor chip 23. Therefore, the interposer may be provided with a pad (not shown) for electrically connecting to the electrode of the semiconductor chip 23 described later. As a result, the pad spacing and the arrangement pattern of the semiconductor chip 23 can be converted, and the degree of freedom in designing the electronic device 1 can be further increased.
As the interposer, for example, a silicon substrate, a ceramic substrate, an inorganic substrate such as a glass substrate, an organic substrate such as a resin substrate, or the like is used.

The insulating layer 21 may be a resin film (organic insulating layer) containing a thermosetting resin or a thermoplastic resin, for example, as a component of the photosensitive resin composition, and is a usual sealing used in the technical field of semiconductors. It may be a stop material.

Examples of the constituent materials of the through wires 221 and 222 include copper or copper alloy, aluminum or aluminum alloy, gold or gold alloy, silver or silver alloy, nickel or nickel alloy, and the like.

The chip-embedded structure 27 produced by a method different from the above may be prepared.

[2] Upper layer wiring layer forming step S2
Next, the upper wiring layer 25 is formed on the insulating layer 21 and the semiconductor chip 23.

[2-1] First Resin Film Arrangement Step S20
First, as shown in FIG. 4B, the photosensitive resin varnish 5 is applied (arranged) on the insulating layer 21 and the semiconductor chip 23. As a result, as shown in FIG. 4C, a liquid film of the photosensitive resin varnish 5 is obtained. The photosensitive resin varnish 5 is the photosensitive resin composition of the present embodiment.

The photosensitive resin varnish 5 is applied using, for example, a spin coater, a bar coater, a spray device, an inkjet device, or the like.

The viscosity of the photosensitive resin varnish 5 is not particularly limited, but is 10 cP to 6000 cP, preferably 20 cP to 5000 cP, and more preferably 30 cP to 4000 cP. When the viscosity of the photosensitive resin varnish 5 is within the above range, a thinner photosensitive resin layer 2510 (see FIG. 4D) can be formed. As a result, the upper wiring layer 25 can be made thinner, and the electronic device 1 can be easily made thinner.
The viscosity of the photosensitive resin varnish 5 is, for example, a value measured using a cone plate type viscometer (TV-25, manufactured by Toki Sangyo) under the condition of a rotation speed of 100 rpm.

Next, the liquid film of the photosensitive resin varnish 5 is dried. As a result, the photosensitive resin layer 2510 shown in FIG. 4D is obtained.

The drying conditions of the photosensitive resin varnish 5 are not particularly limited, and examples thereof include conditions of heating at a temperature of 80 to 150 ° C. for 1 to 60 minutes.

In this step, instead of the process of applying the photosensitive resin varnish 5, a process of arranging the photosensitive resin film formed by forming the photosensitive resin varnish 5 into a film may be adopted. The photosensitive resin film is the photosensitive resin composition of the present embodiment and is a resin film having photosensitivity.

The photosensitive resin film is produced, for example, by applying the photosensitive resin varnish 5 to the ground surface of a carrier film or the like by various coating devices, and then drying the obtained coating film.

After forming the photosensitive resin layer 2510 in this way, the photosensitive resin layer 2510 is heat-treated before exposure, if necessary. By performing the pre-exposure heat treatment, the molecules contained in the photosensitive resin layer 2510 are stabilized, and the reaction in the first exposure step S21 described later can be stabilized. On the other hand, by heating under the heating conditions described later, the adverse effect of heating on the photoacid generator can be minimized.

The temperature of the pre-exposure heat treatment is preferably 70 to 130 ° C, more preferably 75 to 120 ° C, and even more preferably 80 to 110 ° C. If the temperature of the pre-exposure heat treatment is lower than the lower limit, the purpose of stabilizing the molecules by the pre-exposure heat treatment may not be achieved. On the other hand, when the temperature of the pre-exposure heat treatment exceeds the upper limit value, the movement of the photoacid generator becomes too active, and the acid is less likely to be generated even when light is irradiated in the first exposure step S21 described later. However, there is a risk that the processing accuracy of patterning will decrease due to a wide range.

The time of the pre-exposure heat treatment is appropriately set according to the temperature of the pre-exposure heat treatment, but is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and further preferably 3 to 3 at the temperature. It is said to be 6 minutes. If the pre-exposure heat treatment time is less than the lower limit, the heating time is insufficient, and the purpose of stabilizing the molecules by the pre-exposure heat treatment may not be achieved. On the other hand, if the pre-exposure heat treatment time exceeds the upper limit value, the heating time is too long, so that even if the pre-exposure heat treatment temperature is within the above range, the action of the photoacid generator is inhibited. There is a risk that it will end up.

The atmosphere of the heat treatment is not particularly limited. It may be an inert gas atmosphere or a reducing gas atmosphere, but it is considered to be in the atmosphere in consideration of work efficiency and the like.

The atmospheric pressure is not particularly limited. It may be under reduced pressure or pressurized, but it is set to normal pressure in consideration of work efficiency and the like. The normal pressure means a pressure of about 30 to 150 kPa, preferably atmospheric pressure.

[2-2] First exposure step S21
Next, the photosensitive resin layer 2510 is exposed to light.

First, as shown in FIG. 4D, the mask 412 is arranged in a predetermined region on the photosensitive resin layer 2510. Then, light (active radiation) is irradiated through the mask 412. As a result, the photosensitive resin layer 2510 is exposed according to the pattern of the mask 412.

FIG. 4D illustrates the case where the photosensitive resin layer 2510 has so-called negative photosensitive. In this example, the region of the photosensitive resin layer 2510 corresponding to the light-shielding portion of the mask 412 is dissolved in the developing solution.

On the other hand, in the region corresponding to the transmissive portion of the mask 412, active chemical species are generated from the photocationic polymerization initiator. The active species acts as a catalyst for the curing reaction.

The exposure amount in the exposure process is not particularly limited. 100 to 2000 mJ / cm ² is preferable, and 200 to 1000 mJ / cm ² is more preferable. As a result, underexposure and overexposure in the photosensitive resin layer 2510 can be suppressed. As a result, high patterning accuracy can be finally realized.
Then, if necessary, the photosensitive resin layer 2510 is subjected to heat treatment after exposure.

The temperature of the post-exposure heat treatment is not particularly limited. It is preferably 50 to 150 ° C, more preferably 50 to 130 ° C, still more preferably 55 to 120 ° C, and particularly preferably 60 to 110 ° C. By performing the heat treatment after exposure at such a temperature, the catalytic action of the generated acid is sufficiently enhanced, and the thermosetting resin can be reacted sufficiently in a shorter time. By setting the temperature within the above range, it is possible to suppress a decrease in patterning processing accuracy due to the promotion of acid diffusion.
By setting the temperature of the heat treatment after exposure to the above lower limit value or more, the reaction rate of the thermosetting resin can be increased and the productivity can be increased. On the other hand, by setting the temperature of the post-exposure heat treatment to be equal to or lower than the above upper limit value, it is possible to suppress a decrease in patterning processing accuracy due to the promotion of acid diffusion.

The time of the post-exposure heat treatment is appropriately set according to the temperature of the post-exposure heat treatment. At the above temperature, it is preferably 1 to 30 minutes, more preferably 2 to 20 minutes, and even more preferably 3 to 15 minutes. By performing the heat treatment after exposure in such a time, the thermosetting resin can be sufficiently reacted, and the diffusion of acid can be suppressed to prevent the patterning processing accuracy from being lowered.

The atmosphere of the heat treatment after exposure is not particularly limited. It may be an inert gas atmosphere or a reducing gas atmosphere, but it is considered to be in the atmosphere in consideration of work efficiency and the like.

The atmospheric pressure of the post-exposure heat treatment is not particularly limited. It may be under reduced pressure or pressurized, but it is set to normal pressure in consideration of work efficiency and the like. As a result, the pre-exposure heat treatment can be performed relatively easily. The normal pressure means a pressure of about 30 to 150 kPa, preferably atmospheric pressure.

[2-3] First developing step S22
Next, the photosensitive resin layer 2510 is subjected to a developing process. As a result, an opening 423 penetrating the photosensitive resin layer 2510 is formed in the region corresponding to the light-shielding portion of the mask 412 (see FIG. 5E).

Examples of the developing solution include an organic developing solution and a water-soluble developing solution. In this embodiment, the developer preferably contains an organic solvent. More specifically, the developing solution is preferably a developing solution containing an organic solvent as a main component (a developing solution in which 95% by mass or more of the components are organic solvents). By developing with a developer containing an organic solvent, it is possible to suppress swelling of the pattern due to the developer as compared with the case of developing with an alkaline developer (water-based). That is, it is easy to obtain a finer pattern.

Specific examples of the organic solvent that can be used in the developing solution 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. And so on.
As the developing solution, an organic solvent developing solution containing only an organic solvent and containing only impurities inevitably contained may be used. Impurities that are inevitably contained include metal elements and water, but from the viewpoint of preventing contamination of electronic devices, it is better to have a small amount of impurities that are inevitably contained.

The method of bringing the developer into contact with the photosensitive resin layer 2510 is not particularly limited. Generally known dipping method, paddle method, spray method and the like can be appropriately applied.

The time of the developing step is usually in the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film and the shape of the formed pattern.

[2-4] First curing step S23
After the development treatment, the photosensitive resin layer 2510 is subjected to a curing treatment (heat treatment after development). The conditions of the curing treatment are not particularly limited, but the heating temperature is about 160 to 250 ° C. and the heating time is about 30 to 240 minutes. As a result, the photosensitive resin layer 2510 can be cured to obtain the organic insulating layer 251 while suppressing the heat effect on the semiconductor chip 23.

[2-5] Wiring layer forming step S24
Next, the wiring layer 253 is formed on the organic insulating layer 251 (see FIG. 5 (f)). The wiring layer 253 is formed by obtaining a metal layer by a vapor phase film forming method such as a sputtering method or a vacuum vapor deposition method, and then patterning the metal layer by a photolithography method and an etching method.
Prior to the formation of the wiring layer 253, a surface modification treatment such as a plasma treatment may be performed.

[2-6] Second Resin Film Arrangement Step S25
Next, as shown in FIG. 5 (g), the photosensitive resin layer 2520 is obtained in the same manner as in the first resin film arranging step S20. The photosensitive resin layer 2520 is arranged so as to cover the wiring layer 253.
Then, if necessary, the photosensitive resin layer 2520 is heat-treated before exposure. The treatment conditions are, for example, the conditions described in the first resin film arranging step S20.

[2-7] Second exposure step S26
Next, the photosensitive resin layer 2520 is exposed to light. The processing conditions are, for example, the conditions described in the first exposure step S21.
Then, if necessary, the photosensitive resin layer 2520 is heat-treated after exposure. The processing conditions are, for example, the conditions described in the first exposure step S21.

[2-8] Second developing step S27
Next, the photosensitive resin layer 2520 is subjected to a developing process. The processing conditions are, for example, the conditions described in the first developing step S22. As a result, an opening 424 penetrating the photosensitive resin layers 2510 and 2520 is formed (see FIG. 5 (h)).

[2-9] Second curing step S28
After the development treatment, the photosensitive resin layer 2520 is subjected to a curing treatment (heat treatment after development). The curing conditions are, for example, the conditions described in the first curing step S23. As a result, the photosensitive resin layer 2520 is cured to obtain an organic insulating layer 252 (see FIG. 6 (i)).

In the present embodiment, the upper wiring layer 25 has two layers of the organic insulating layer 251 and the organic insulating layer 252, but may have three or more layers. In this case, after the second curing step S28, a series of steps from the wiring layer forming step S24 to the second curing step S28 may be repeatedly added.

[2-10] Through wiring forming step S29
Next, the through wiring 254 shown in FIG. 6 (i) is formed in the opening 424.

A known method is used for forming the through wiring 254, and for example, the following method is used.

First, a seed layer (not shown) is formed on the organic insulating layer 252. The seed layer is formed on the upper surface of the organic insulating layer 252 together with the inner surface (side surface and bottom surface) of the opening 424.
As the seed layer, for example, a copper seed layer is used. Further, the seed layer is formed by, for example, a sputtering method.
The seed layer may be made of the same kind of metal as the through wiring 254 to be formed, or may be made of a different kind of metal.

Next, among the seed layers (not shown), a resist layer (not shown) is formed on a region other than the opening 424. Then, using this resist layer as a mask, the opening 424 is filled with metal. For this filling, for example, an electrolytic plating method is used. Examples of the metal to be filled include copper or copper alloy, aluminum or aluminum alloy, gold or gold alloy, silver or silver alloy, nickel or nickel alloy and the like. In this way, the conductive material is embedded in the opening 424 to form the through wiring 254.

Then, a resist layer (not shown) is removed. Further, a seed layer (not shown) on the organic insulating layer 252 is removed. For this, for example, a flash etching method can be used.
The formation location of the through wiring 254 is not limited to the position shown in the figure.

[3] Substrate peeling step S3
Next, as shown in FIG. 6 (j), the substrate 202 is peeled off. As a result, the lower surface of the insulating layer 21 is exposed.

[4] Lower layer wiring layer forming step S4
Next, as shown in FIG. 6 (k), the lower wiring layer 24 is formed on the lower surface side of the insulating layer 21. The lower layer wiring layer 24 may be formed by any method, and may be formed in the same manner as, for example, the above-mentioned upper layer wiring layer forming step S2.
The lower layer wiring layer 24 formed in this way is electrically connected to the upper layer wiring layer 25 via the through wiring 221.

[5] Solder bump forming step S5
Next, as shown in FIG. 6 (L), the solder bumps 26 are formed on the lower wiring layer 24. Further, a protective film such as a solder resist layer may be formed on the upper wiring layer 25 and the lower wiring layer 24, if necessary.
As described above, the through electrode substrate 2 is obtained.

The through silicon via substrate 2 shown in FIG. 6 (L) can be divided into a plurality of regions. Therefore, for example, by individualizing the through electrode substrates 2 along the alternate long and short dash line shown in FIG. 6 (L), a plurality of through electrode substrates 2 can be efficiently manufactured. For individualization, for example, a diamond cutter or the like can be used.

[6] Laminating step S6
Next, the semiconductor package 3 is arranged on the individualized through electrode substrate 2. As a result, the electronic device 1 shown in FIG. 1 is obtained.

Such a method for manufacturing the electronic device 1 can be applied to a wafer level process or a panel level process using a large-area substrate. As a result, the manufacturing efficiency of the electronic device 1 can be increased and the cost can be reduced.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. As a reminder, the invention is not limited to examples.

<Synthesis of polymer (for comparative example)>
(Synthesis of polymer (A-6))
In a 2 L separable flask, 428 g of γ-butyrolactone, 155.11 g of 4,4'-oxydiphthalic dianhydride and 130.14 g of 2-hydroxyethyl methacrylate were weighed and stirred at room temperature to completely dissolve them. Subsequently, 79.1 g of pyridine was added while stirring at room temperature, and the mixture was further stirred at room temperature for 16 hours.
Next, while cooling and stirring the above solution under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide in 206 g of γ-butyrolactone was added over 30 minutes. Subsequently, 120.1 g of 4,4'-diaminodiphenyl ether and 240 g of γ-butyrolactone were added, and stirring was further continued at room temperature for 2 hours.
After completion of the reaction, 30 g of ethyl alcohol was added and the mixture was stirred for 1 hour. Then, 400 g of γ-butyrolactone was added and further stirred, and the resulting precipitate was removed by filtration. As a result, a polymer reaction solution was obtained.
The obtained reaction solution was added dropwise to a large amount of 30% by mass methanol solution at room temperature with stirring to precipitate a polymer. The obtained precipitate was collected by filtration and vacuum dried to obtain a polymer (A-6).
The weight average molecular weight (Mw) of this polymer (A-6) measured by GPC was 18,000.

<Preparation of photosensitive resin composition>
Each of the raw materials formulated according to Table 1 below was stirred at room temperature until the raw materials were completely dissolved to obtain a solution. Then, the solution was filtered through a polyethylene filter having a pore size of 0.2 μm. In this way, a varnish-like photosensitive resin composition was obtained.

The details of the raw materials of each component in Table 1 are as follows.

(Epoxy resin or comparative resin)
(A-1) Epoxy resin "NC3500" manufactured by Nippon Kayaku Co., Ltd.
(A-2) Epoxy resin "NC3000" manufactured by Nippon Kayaku Co., Ltd.
(A-3) Epoxy resin "TC-5500E" manufactured by Nippon Steel & Sumitomo Metal Corporation
(A-4) Epoxy resin "EOCN-1020-55" manufactured by Nippon Kayaku Co., Ltd.
(A-5) Epoxy resin "EPPN-201" manufactured by Nippon Kayaku Co., Ltd.
(A-6) Polyimide resin synthesized above (for comparative example)

(Photocationic polymerization initiator)
(B-1) CPI-310B (manufactured by Sun Appro)
(B-2) Irugure OXE01 (manufactured by BASF)

(Phenoxy resin)
(C-1) JER-1256 (manufactured by Mitsubishi Chemical Corporation)

(Adhesion aid)
(D-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)
(D-2) KBM-403E (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant)
(E-1) FC4432 (manufactured by 3M, fluorine-based)

(solvent)
(F-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA)
(F-2) γ-Butyrolactone (GBL)

The chemical structures of the epoxy resin, photocationic polymerization initiator, phenoxy resin and adhesion aid are shown below.
In the following epoxy resin structure, n indicates that two or more structural units enclosed in parentheses are present in the epoxy resin. Further, in the epoxy resin (A-1), when m is 2, the epoxy resin (A-1) contains a diglycidyloxybenzene skeleton.

<Evaluation of curing shrinkage rate>
The photosensitive resin composition was spin-coated on an 8-inch silicon wafer so that the film thickness after drying was 10 μm. Subsequently, it was heated at 120 ° C. for 3 minutes to obtain a photosensitive resin film. The film thickness at this time is measured and used as the film thickness A.
The obtained photosensitive resin film was exposed to ^{1000 mJ / cm 2} with a high-pressure mercury lamp. Then, it was exposed at 120 ° C. for 3 minutes, baked, and then immersed in cyclopentanone for 30 seconds. After that, it was cured by heat treatment at 170 ° C. for 90 minutes in a nitrogen atmosphere. From the above, a cured product of the photosensitive resin composition was obtained. The film thickness at this time is measured and is defined as the film thickness B.
The curing shrinkage rate was calculated by substituting the film thickness A and the film thickness B into the following equations. The curing shrinkage rate is preferably small in order to maintain flatness after application on the wiring.
Curing shrinkage rate [%] = {(film thickness A-film thickness B) / film thickness A} x 100

<Evaluation of glass transition temperature (Tg)>
(Preparation of test piece for measuring glass transition temperature (Tg))
The photosensitive resin composition was spin-coated on an 8-inch silicon wafer so that the film thickness after drying was 10 μm, and then heated at 120 ° C. for 3 minutes to obtain a photosensitive resin film.
The obtained photosensitive resin film was exposed to ^{1000 mJ / cm 2} with a high-pressure mercury lamp. Then, it was exposed at 120 ° C. for 3 minutes, baked, and then immersed in cyclopentanone for 30 seconds. After that, it was cured by heat treatment at 170 ° C. for 90 minutes in a nitrogen atmosphere. From the above, a cured product of the photosensitive resin composition was obtained.
The obtained cured product was cut with a dicing saw so as to have a width of 5 mm, and was peeled off from the substrate by immersing it in a 2% hydrofluoric acid aqueous solution. The peeled film was dried at 60 ° C. for 10 hours to obtain a test piece (30 mm × 5 mm × 10 μm thickness).

(Measurement of glass transition temperature (Tg))
Using a thermomechanical analyzer (TMA / SS6000, manufactured by Seiko Instruments), the obtained test piece was heated to 300 ° C. at a heating rate of 10 ° C./min, and the coefficient of thermal expansion of the obtained test piece was measured. It was measured.
Then, based on the obtained measurement results, the glass transition temperature (Tg) of the cured product was calculated from the inflection point of the coefficient of thermal expansion. The unit of Tg is ° C. Those in which no inflection point was observed in the coefficient of thermal expansion were evaluated as Tg> 300 ° C.

<Evaluation of insulation reliability>
(Preparation of sample for insulation reliability)
A Cu wiring substrate in which a comb-tooth type Cu wiring having a width of 5 μm / pitch of 5 μm and a height of 5 μm was formed on a silicon wafer with an oxide film was produced.
The photosensitive resin composition was applied onto the Cu wiring substrate by spin coating so that the film thickness after drying was 10 μm, and dried at 120 ° C. for 3 minutes to form a photosensitive resin film.
The obtained photosensitive resin film was exposed to ^{1000 mJ / cm 2} using a high-pressure mercury lamp. Then, it was exposed at 120 ° C. for 3 minutes, baked, and then immersed in cyclopentanone for 30 seconds. Then, it was heat-treated at 170 ° C. for 90 minutes in a nitrogen atmosphere to obtain a cured film. This was used as a sample for insulation reliability evaluation.

(Insulation reliability evaluation)
A simulated electronic device for evaluation was produced by solder-connecting the end (Cu electrode) of the Cu wiring of the substrate produced in the above (preparation of sample for insulation reliability) and the electrode wiring. This was placed in an environment of 130 ° C./85% RH while biasing 3.5 V with a B-HAST apparatus.
Automatically measuring the insulation resistance between the Cu wiring board Cu wiring 6 minute intervals, a case where the insulation resistance is less than 1.0 × 10 ⁴ Ω to dielectric breakdown. Then, the time (h) from the start of the test to the dielectric breakdown was measured.
In the table below, the case where this time is 210 hours or more is marked with ⊚, and the case where this time is less than 48 hours is marked with ×.

<Evaluation of tensile elongation>
First, a test piece was prepared in the same manner as in the above-mentioned "Preparation of a test piece for measuring the glass transition temperature (Tg)".
The obtained test piece was subjected to a tensile test using a tensile tester (Tencilon RTC-1210A manufactured by Orientec Co., Ltd.) in an atmosphere of 23 ° C. by a method conforming to JIS K 7161 to determine the tensile elongation of the test piece. It was measured. The stretching speed in the tensile test was 5 mm / min. The unit of tensile elongation is%.

<Evaluation of patterning property>
The photosensitive resin composition was applied onto an 8-inch silicon wafer using a spin coater so that the film thickness after drying was 5 μm. Then, it was dried on a hot plate at 100 ° C. for 3 minutes to obtain a photosensitive resin film (photosensitive resin film A).
An i-line stepper (Nikon NSR-4425i) is passed through this photosensitive resin film through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a punching pattern having a width of 0.5 to 50 μm are drawn). ) Was used to irradiate i-rays while changing the exposure amount.
After irradiation with i-ray, additional heating is performed at 130 ° C. for 5 minutes, then developed with cyclopentanone as a developing solution for 30 seconds, spun at 2500 rpm for 10 seconds to dry, and a post-developed film (negative pattern). Got
The film thickness is plotted against the exposure amount, and the film thickness difference between the photosensitive resin film and the developed film of the remaining pattern of 50 μm square is 0.3 μm or less, and the exposure amount with the 5 μm round vialess pattern opened. It was evaluated as sensitivity (mJ / cm ^2). It is desirable that the sensitivity is small from the viewpoint of throughput.
In the table below, the case where the sensitivity is 1000 mJ / cm ² or less is marked with ⊚, and the case where ^{the sensitivity is 1000 mJ / cm 2} or more and 2000 mJ / cm ² or less is marked with ◯.

<Evaluation of flatness during application>
A Cu wiring board in which Cu wiring having a width of 5 μm, a pitch of 5 μm, and a height of 5 μm was formed on a silicon wafer with an oxide film was produced.
The photosensitive resin composition was applied onto a Cu wiring substrate by spin coating so that the film thickness after drying was 10 μm, and dried at 120 ° C. for 3 minutes to form a photosensitive resin film. The substrate with the photosensitive resin film was cracked, the cross section was polished, and the unevenness of the surface of the photosensitive resin film was evaluated by SEM observation of the cross section.
In the table below, those with surface irregularities of 1 μm or less were evaluated as ◯, and those with surface irregularities exceeding 1 μm were evaluated as x.

Table 1 summarizes the composition of the raw materials of each composition and the above evaluation results.

From Table 1, by using an epoxy resin containing a biphenyl skeleton and a glycidyloxybenzene skeleton and using a chemically amplified photosensitive resin composition, sufficient heat resistance is sufficient even if the heating temperature during the curing treatment is low. It was shown that a cured film having an epoxy can be obtained and the shrinkage of the film during the curing treatment can be suppressed.

1 Electronic device 1A Electronic device 1B Electronic device 2 Through electrode substrate 3 Semiconductor package 5 Photosensitive resin varnish 21 Insulation layer 23 Semiconductor chip 24 Lower layer wiring layer 24A Lower layer wiring layer 24B Lower layer wiring layer 25 Upper layer wiring layer 26 Solder bump 27 Chip embedded Structure 31 Package substrate 32 Semiconductor chip 33 Bonding wire 34 Sealing layer 35 Solder bump 202 Board 221 Through wiring 222 Through wiring 231 Land 240 Organic insulation layer 241 Organic insulation layer 242 Organic insulation layer 243 Wiring layer 245 Bump adhesion layer 251 Organic insulation Layer 252 Organic Insulation Layer 253 Wiring Layer 254 Through Wiring 412 Mask 423 Opening 424 Opening 2510 Photosensitive Resin Layer 2520 Photosensitive Resin Layer S1 Chip Arrangement Step S2 Upper Wiring Layer Forming Step S20 First Resin Film Arrangement Step S21 First Exposure Step S22 1st development step S23 1st curing step S24 Wiring layer forming step S25 2nd resin film placement step S26 2nd exposure step S27 2nd developing step S28 2nd curing step S29 Through wiring forming step S3 Substrate peeling step S4 Lower layer wiring Layer forming step S5 Solder bump forming step S6 Laminating step W Diameter

Claims (13)

A photosensitive resin composition containing an epoxy resin (A1) containing a biphenyl skeleton and a glycidyloxybenzene skeleton, which is a chemically amplified type. The photosensitive resin composition according to claim 1.
The glycidyloxybenzene skeleton is a photosensitive resin composition containing a diglycidyloxybenzene skeleton. The photosensitive resin composition according to claim 1 or 2.
The epoxy resin (A1) is a photosensitive resin composition containing a structural unit represented by the following general formula (1).

In the general formula (1)
R is a glycidyloxy group
m is an integer of 1 to 3. The photosensitive resin composition according to any one of claims 1 to 3.
A photosensitive resin composition containing, as the epoxy resin (A1), an epoxy resin containing a biphenyl skeleton and a monoglycidyloxybenzene skeleton, and an epoxy resin containing a biphenyl skeleton and a diglycidyloxybenzene skeleton. The photosensitive resin composition according to any one of claims 1 to 4.
Further, a photosensitive resin composition containing an epoxy resin (A2) different from the epoxy resin (A1). The photosensitive resin composition according to any one of claims 1 to 5.
A photosensitive resin composition further containing a phenoxy resin. The photosensitive resin composition according to any one of claims 1 to 6.
A photosensitive resin composition further containing a photocationic polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 7.
A photosensitive resin composition further containing an adhesion aid. The photosensitive resin composition according to any one of claims 1 to 8.
A photosensitive resin composition that is a negative type. The photosensitive resin composition according to any one of claims 1 to 9.
A photosensitive resin composition used for forming an insulating layer in a rewiring layer in an electronic device. A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 10.
The exposure step of exposing the photosensitive resin film and
A developing process for developing the exposed photosensitive resin film, and
Manufacturing methods for electronic devices, including. The method for manufacturing an electronic device according to claim 11.
A method for manufacturing an electronic device, which comprises a thermosetting step of heating and curing the exposed photosensitive resin film after the developing step. An electronic device comprising a cured film of the photosensitive resin composition according to any one of claims 1 to 10.

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