JP2020056809A - Negative photosensitive resin composition and semiconductor device - Google Patents

Abstract

To provide a negative photosensitive resin composition excellent in low-temperature curability, reflow-resistance and sensitivity.SOLUTION: A negative photosensitive resin composition of the present invention has an epoxy resin, a phenoxy resin, a photoacid generator, and a thermal acid generator containing a predetermined aromatic sulfonium salt. The negative photosensitive resin composition is used for forming a film.SELECTED DRAWING: None

Description

  The present invention relates to a negative photosensitive resin composition and a semiconductor device.

  Until now, various developments have been made on photosensitive resin compositions. As this type of technology, for example, a technology described in Patent Document 1 is known. Patent Literature 1 describes a photosensitive resin composition containing an epoxy resin, a phenol resin, and a photopolymerization initiator (Table 1 of Patent Literature 1).

WO2014 / 010204

  However, as a result of the study by the present inventors, it has been found that the photosensitive resin composition described in Patent Document 1 has room for improvement in low-temperature curability, reflow resistance and sensitivity.

  The present inventor further examined that, in a negative photosensitive resin composition using an epoxy resin, a phenoxy resin and a photoacid generator, a thermal acid generator containing an aromatic sulfonium salt was used in combination to improve the low-temperature curability. However, they found that the reflow resistance and the sensitivity were improved, and completed the present invention.

（上記一般式（１）中、
Ｒ^１は水素原子、メトキシカルボニル基、アセチル基、ベンゾイル基のいずれか示し、
Ｒ^２は水素原子、ハロゲン原子、炭素数１〜４のアルキル基のいずれかを示し、
Ｒ^３は炭素数１〜４のアルキル基、炭素数１〜４のアルキル基で置換もしくは無置換のベンジル基またはα−ナフチルメチル基のいずれかを示し、
Ｒ^４は炭素数１〜４のアルキル基を示す。
ＸはＳｂＦ_６、ＰＦ_６、ＡｓＦ_６、ＢＦ_４、ＣＦ_３ＳＯ_３、（ＣＦ_３ＳＯ_２）_２Ｎ、Ｂ（Ｃ_６Ｆ_５）_４のいずれかを示す。） According to the present invention,
A negative photosensitive resin composition for film formation,
Epoxy resin,
Phenoxy resin,
A photoacid generator,
A thermal acid generator containing an aromatic sulfonium salt represented by the following general formula (1),
And a negative photosensitive resin composition comprising:

(In the general formula (1),
R ¹ represents any ^one of a hydrogen atom, a methoxycarbonyl group, an acetyl group, and a benzoyl group;
R ² represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
R ³ represents an alkyl group having 1 to 4 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, or an α-naphthylmethyl group;
R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.
X represents any one of SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , (CF ₃ SO ₂ ) ₂ N, and B (C ₆ F ₅ ) ₄ . )

According to the present invention,
A semiconductor chip,
A redistribution layer provided on the surface of the semiconductor chip,
There is provided a semiconductor device, wherein the insulating layer in the rewiring layer is made of a cured product of the negative photosensitive resin composition.

  According to the present invention, a negative photosensitive resin composition excellent in low-temperature curability, reflow resistance and sensitivity, and a semiconductor device using the same are provided.

FIG. 1 is a longitudinal sectional view illustrating an example of a configuration of a semiconductor device according to an embodiment. FIG. 2 is a partially enlarged view of a region surrounded by a chain line in FIG. FIG. 2 is a process chart showing a method for manufacturing the semiconductor device shown in FIG. 1. FIG. 2 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 2 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 2 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 9 is a partially enlarged cross-sectional view illustrating a first modification of the semiconductor device according to the embodiment. FIG. 10 is a partially enlarged cross-sectional view illustrating a second modification of the semiconductor device according to the embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will not be repeated. Also, the figure is a schematic view, and does not match the actual dimensional ratio.

The outline of the photosensitive resin composition of the present embodiment will be described.
The photosensitive resin composition of the present embodiment includes an epoxy resin, a phenoxy resin, a photoacid generator, a thermal acid generator containing a predetermined aromatic sulfonium salt, and a negative photosensitive resin composition for film formation. It is.

  According to the findings of the present inventor, by using a thermal acid generator containing an aromatic sulfonium salt and a photoacid generator in combination, a general curing temperature of about 230 ° C., which is much lower than 170 ° C. Also showed good curing properties, that is, low-temperature curability. Although the detailed mechanism is not clear, it is considered that the sensitivity is increased because the acid is generated from the photoacid generator at the time of exposure and the acid is slightly generated from the thermal acid generator.

  Accordingly, the negative photosensitive resin composition of the present embodiment (hereinafter, may be simply referred to as “photosensitive resin composition”) has excellent sensitivity at low temperatures while being excellent in sensitivity. The reflow resistance when using the cured film cured by the method can be improved.

  According to the photosensitive resin composition of the present embodiment, since the heat resistance and the patterning property can be improved, a semiconductor device having excellent connection reliability and an electronic device using the same can be realized.

  In addition, the photosensitive resin composition of the present embodiment is expected to be suitably used for forming an insulating layer of a rewiring layer formed on a semiconductor chip or the like.

  The resin film of the photosensitive resin composition of the present embodiment is used as a permanent film, a protective film, an insulating film, a rewiring material, and the like in an electric / electronic device (electronic device). This resin film includes a cured film cured by heating.

  Here, “electrical / electronic equipment” means 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, and other electronic devices. It refers to elements, devices, end products, and other general equipment related to electricity that apply engineering technology.

  Among them, the photosensitive resin composition of the present embodiment can be suitably used, for example, as a photosensitive resin composition for a bump protective film. A resin film provided around an electrical connection element such as a bump, a land, and a wiring is collectively referred to as a “bump protection film”. The photosensitive resin composition for a bump protective film refers to a resin composition used for forming a bump protective film.

  Specific examples of the bump protection film include, for example, a passivation film, an overcoat film, and an interlayer insulating film provided around the electric connection element. Although the resin film is provided on the semiconductor chip, it may be provided close to the semiconductor chip, and may be provided at a position away from the semiconductor chip such as a rewiring layer or a build-up wiring layer. It may be provided.

Next, details of the photosensitive resin composition of the present embodiment will be described.
(Epoxy resin)
The photosensitive resin composition of the present embodiment contains an epoxy resin. Thereby, film physical properties and workability of the resin film of the photosensitive resin composition can be improved.

As the epoxy resin, 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, and the molecular weight and molecular structure are not particularly limited.
Examples of the epoxy resin include phenol novolak type epoxy resin, cresol novolak type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenoxy resin, naphthalene skeleton type epoxy resin, 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, aromatic poly Functional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, polyfunctional alicyclic epoxy resin, etc. It is. The epoxy resins may be used alone or in combination.

  The epoxy resin can include a solid epoxy resin having two or more epoxy groups in a molecule. As the solid epoxy resin, those having two or more epoxy groups and being solid at 25 ° C. (room temperature) can be used. Thereby, the mechanical properties of the resin film of the photosensitive resin composition can be improved.

  Further, the epoxy resin may include a polyfunctional epoxy resin having three or more functional groups in a molecule (that is, a polyfunctional epoxy resin having three or more epoxy groups in one molecule).

  Examples of the trifunctional or higher polyfunctional epoxy resin include, for example, phenol novolak epoxy resin, cresol novolak epoxy resin, triphenylmethane epoxy resin, dicyclopentadiene epoxy resin, bisphenol A epoxy resin, and tetramethylbisphenol F It preferably contains one or more epoxy resins selected from the group consisting of epoxy resins, and more preferably contains novolak epoxy resins. Thereby, an appropriate coefficient of thermal expansion can be realized while increasing the heat resistance of the resin film.

  Further, the epoxy resin may include a liquid epoxy resin having two or more epoxy groups in a molecule. The liquid epoxy resin functions as a filming agent and can improve the brittleness of the resin film of the photosensitive resin composition.

  As the liquid epoxy resin, an epoxy compound having two or more epoxy groups and being liquid at room temperature of 25 ° C. can be used. The viscosity at 25 ° C. of the 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, at least one 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 them, 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 to 200 g / eq, preferably 105 g / eq to 180 g / eq, and more preferably 110 g / eq to 170 g / eq. Thereby, the brittleness of the resin 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, more preferably 15% by mass or more, based on the entire 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, more preferably 30% by mass, based on the whole nonvolatile components of the photosensitive resin composition. It is as follows. This makes it possible to balance the film characteristics of the cured film.

  The lower limit of the content of the epoxy resin is, for example, 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, based on the entire nonvolatile components of the photosensitive resin composition. is there. Thereby, the heat resistance and mechanical strength of the finally obtained cured film can be improved. On the other hand, the upper limit of the content of the epoxy resin is, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, based on the entire nonvolatile components of the photosensitive resin composition. It is. Thereby, the patterning property can be improved.

  In the present embodiment, the non-volatile component of the photosensitive resin composition refers to a residue excluding volatile components such as water and a solvent. The content of the photosensitive resin composition relative to the entire non-volatile component, when containing a solvent, refers to the content of the photosensitive resin composition relative to the entire non-volatile component excluding the solvent.

  The weight average molecular weight (Mw) of the epoxy resin is not particularly limited, but is preferably, for example, 300 to 9000, and more preferably 500 to 8000. By using a relatively low molecular weight epoxy resin, the reactivity at the time of exposure can be increased.

  In addition, the photosensitive resin composition of the present embodiment may contain a thermosetting resin other than the epoxy resin. Other thermosetting resins include, for example, resins having a triazine ring such as urea (urea) resin and melamine resin; unsaturated polyester resins; maleimide resins such as bismaleimide compounds; polyurethane resins; diallyl phthalate resins; Benzoxazine resin; polyimide resin; polyamide imide resin; benzocyclobutene resin, cyanate ester resin such as cyanate resin such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin. And the like. These may be used alone or in combination of two or more.

(Phenoxy resin)
The photosensitive resin composition of the present embodiment contains a phenoxy resin. Thereby, the flexibility of the resin film of the photosensitive resin composition can be increased.

  The weight average molecular weight (Mw) of the phenoxy resin is not particularly limited, but is, for example, preferably from 10,000 to 100,000, and more preferably from 20,000 to 80,000. By using such a phenoxy resin having a relatively high molecular weight, it is possible to impart good flexibility to the resin film and to impart sufficient solubility to a solvent.

  In the present embodiment, the weight average molecular weight is measured, for example, as a polystyrene equivalent value by gel permeation chromatography (GPC).

  Further, 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 capable of undergoing a crosslinking reaction with the epoxy group in the epoxy resin. By using such a phenoxy resin, solvent resistance and heat resistance in the resin film can be improved.

  Further, as the phenoxy resin, a resin which is solid at 25 ° C. is preferably used. Specifically, a phenoxy resin having a nonvolatile 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.

  As the phenoxy resin, for example, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, copolymerized phenoxy resin of bisphenol A type and bisphenol F type, biphenyl type phenoxy resin, bisphenol S type phenoxy resin, biphenyl type phenoxy resin and A phenoxy resin copolymerized with a bisphenol S-type phenoxy resin, and the like, and one or a mixture of two or more thereof are used. Among these, a bisphenol A type phenoxy resin or a copolymerized phenoxy resin of bisphenol A type and bisphenol F type is preferably used.

  The lower limit of the content of the phenoxy resin is, for example, 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more with respect to the epoxy resin content. Thereby, flexibility can be improved. On the other hand, the upper limit of the content of the phenoxy resin is, for example, 60 parts by mass or less, preferably 55 parts by mass or less, more preferably 50 parts by mass or less with respect to the epoxy resin content. Thereby, the solubility of the phenoxy resin is increased, and a photosensitive resin composition having excellent coatability can be realized.

  In addition, the photosensitive resin composition of this embodiment may contain a thermoplastic resin other than the above-mentioned phenoxy resin. Examples of the thermoplastic resin include a polyvinyl acetal resin, an acrylic resin, a polyamide resin (eg, nylon), a thermoplastic urethane resin, a polyolefin resin (eg, polyethylene, polypropylene), a polycarbonate, a polyester resin (eg, polyethylene terephthalate). , Polybutylene terephthalate, etc.), polyacetal, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, fluororesin (eg, polytetrafluoroethylene, polyvinylidene fluoride, etc.), modified polyphenylene ether, polysulfone, polyethersulfone, polyarylate, polyamide Examples include imide, polyetherimide, and thermoplastic polyimide. These may be used alone or in combination of two or more.

(Photoacid generator)
The photosensitive resin composition of the present embodiment contains a photoacid generator. As a result, workability during patterning, such as sensitivity and resolution, can be improved.
The photosensitive resin composition of the present embodiment is a chemically amplified photosensitive resin composition using an acid generated from a photoacid generator as a catalyst, and can be used as a negative photosensitive resin composition.

  Examples of the photoacid generator include an onium salt compound. More specifically, diazonium salts, iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, triarylbilium salts, benzylpyridinium thiocyanates, dialkylphenacylsulfonium salts, dialkylhydroxyphenylphosphonium salts and the like Cationic photopolymerization initiators and the like. Among them, a triarylsulfonium salt can be used from the viewpoint of patterning properties.

  As the counter anion of the onium salt compound, a borate anion, a sulfonate anion, a gallate anion, a phosphorus-based anion, an antimony-based anion, or the like is used. Among these, from the viewpoint of insulation reliability, it is preferable to include an onium gallate salt having a triarylsulfonium cation and a gallate anion as the photoacid generator.

  As these onium salts, commercially available products may be used, and specific examples thereof include Sun-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, and SI-L. L150, SI-L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, union carbide) CPI-100P, CPI-101A, CPI-200K, CPI-200S, CPI-210S, CPI-310B, CPI-310FG, CPI-410S (all manufactured by San-Apro Co., Ltd.), Adeka Optomer SP- 150, SP-151, SP-170, SP-171 (all manufactured by Asahi Denka Kogyo KK), Irga 261 (manufactured by BASF), CI-2481, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (all manufactured by Sartomer) DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI- 100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB -201, BBI-101, BBI-102, BBI-103, BBI-109 (above, mid Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.) and the like. Can be.

The content of the photoacid generator is, for example, 0.3% by mass to 5.0% by mass, and preferably 0.5% by mass to 4.5% by mass, based on the entire solid content of the photosensitive resin composition. %, More preferably 1.0% to 4.0% by mass. By setting the lower limit or more, the patterning property can be improved. On the other hand, by setting the lower limit or less, insulation reliability can be improved.
In the present specification, “to” indicates that an upper limit and a lower limit are included unless otherwise specified.

  The photosensitive resin composition of the present embodiment may contain a photosensitizer other than the photoacid generator.

  The photosensitive resin composition of the present embodiment contains a thermal acid generator containing an aromatic sulfonium salt represented by the following general formula (1). These may be used alone or in combination of two or more.

In the general formula (1),
R ¹ represents any ^one of a hydrogen atom, a methoxycarbonyl group, an acetyl group, and a benzoyl group;
R ² represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
R ³ represents an alkyl group having 1 to 4 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, or an α-naphthylmethyl group;
R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.
X represents any one of SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , (CF ₃ SO ₂ ) ₂ N, and B (C ₆ F ₅ ) ₄ .

The thermal acid generator preferably contains, as an aromatic sulfonium salt, a sulfonium salt borate salt in which X in the general formula (1) represents BF ₄ or B (C ₆ F ₅ ) ₄ . By using a sulfonium salt borate salt, it is possible to enhance the low-temperature curability in a system containing an epoxy resin and a phenol resin.

  The lower limit of the content of the thermal acid generator is, for example, 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more based on 100% by mass of the epoxy resin. is there. Thereby, low-temperature curability and sensitivity can be improved. On the other hand, the upper limit of the content of the thermal acid generator is, for example, 3% by mass or less, preferably 3.5% by mass or less, more preferably 2% by mass or less based on 100% by mass of the epoxy resin. A decrease in the glass transition temperature and a decrease in the 5% weight loss temperature can be suppressed. Although the detailed mechanism is not clear, it is considered that the effect of sublimation of the thermal acid generator can be suppressed by setting the amount of the thermal acid generator used within an appropriate range.

(Surfactant)
The photosensitive resin composition of the present embodiment can include 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. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, an alkyl-based surfactant, and an acrylic-based surfactant.

  The surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. Thereby, in addition to obtaining a uniform resin film (improvement of coating property) and improvement of developing property, it 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. Examples of commercially available products that can be used as a surfactant include, for example, F-251, F-253, F-281, F-430, F-478, and F-551 of the “Mega Fac” 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. Surfactants having a fluorine-containing oligomer structure, fluorine-containing nonionic surfactants such as Neogent 250 and Phantagent 251 manufactured by Neos Co., Ltd., and SILFOAM (registered trademark) series manufactured by Wacker Chemie (eg, SD) 100 TS, SD 670, SD 850, SD 860, and SD 882).

  The content of the surfactant can be, for example, 0.001 to 1% by mass, and preferably 0.005 to 0.5% by mass, based on the total amount of the non-volatile components of the photosensitive resin composition. .

(Adhesion aid)
The photosensitive resin composition of the present embodiment can include an adhesion aid. Thereby, the adhesiveness with the inorganic material can be further improved.

  The adhesion aid is not particularly limited, but for example, a silane coupling agent such as aminosilane, epoxy silane, acryl silane, mercapto silane, vinyl silane, ureido silane, 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 epoxy silane (that is, a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule).

Examples of the amino group-containing coupling agent include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Examples include methyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like.
Examples of the epoxy group-containing coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidylpropyl Trimethoxysilane and the like.
Examples of the acryl group-containing coupling agent or the methacryl group-containing coupling agent include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane And the like.
Examples of the mercapto group-containing coupling agent include 3-mercaptopropyltrimethoxysilane.
Examples of the vinyl group-containing coupling agent include vinyl tris (β-methoxyethoxy) silane, vinyl triethoxy silane, and vinyl trimethoxy silane.
Examples of the ureido group-containing coupling agent include 3-ureidopropyltriethoxysilane.
Examples of the sulfide group-containing coupling agent include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.
Examples of the acid anhydride-containing coupling agent include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride.

  Here, the silane coupling agent is listed, but a titanium coupling agent, a zirconium coupling agent, or the like may be used.

  The content of the adhesion aid is, for example, preferably from 0.3 to 5% by mass, and more preferably from 0.4 to 4% by mass based on the total amount of the non-volatile components of the photosensitive resin composition. Is more preferable, and can be set to 0.5 to 3% by mass.

(Additive)
Other additives may be added to the photosensitive resin composition of the present embodiment, if necessary, in addition to the above components. Examples of other additives include an antioxidant, a filler such as silica, a sensitizer, and a film-forming agent.

(solvent)
The photosensitive resin composition of the present embodiment can include a solvent. The solvent may include an organic 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 chemically react with each component.

  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, dipropylene glycol methyl-n-propyl ether, butyl acetate, and γ-butyrolactone. These may be used alone or in combination.

  The solvent is preferably used such that the concentration of all the nonvolatile components in the photosensitive resin composition is, for example, 30 to 75% by mass. Within this range, each component can be sufficiently dissolved, and good coatability can be ensured. Further, by adjusting the content of the nonvolatile component, the viscosity of the photosensitive resin composition can be appropriately controlled.

  The viscosity of the varnish-shaped photosensitive resin composition at 25 ° C. is, for example, 10 cP to 6000 cP, preferably 20 cP to 5000 cP, and more preferably 30 cP to 4000 cP. By setting the viscosity within the above numerical range, the thickness of the coating film can be appropriately controlled. For example, a thickness of, for example, 1 μm to 100 μm, preferably 3 μm to 80 μm, and more preferably 5 μm to 50 μm can be realized.

  The photosensitive resin composition of the present embodiment has a low-temperature curing property of, for example, 97% or more, preferably 98% or more, more preferably 99% or more, measured at 170 ° C. by the following procedure. Can be. Thereby, even when the heat treatment temperature in the manufacturing process is low, sufficient curability can be exhibited as compared with the case where the heat treatment is performed at a high temperature, so that a decrease in reflow resistance during low temperature heat treatment can be suppressed.

(procedure)
(1) The negative photosensitive resin composition is applied on a silicon wafer having a diameter of 8 inches by spin coating so that the film thickness becomes 8 μm after drying, and dried in air at 100 ° C. for 3 minutes. A photosensitive resin film is formed.
(2) The photosensitive resin film obtained in the above (1) is entirely exposed at 600 mJ / cm ² using an i-line stepper. Subsequently, the substrate is heated after exposure at 70 ° C. for 5 minutes in the air using a hot plate.
(3) The photosensitive resin film obtained in the above (2) is heated at 170 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film A. Further, the photosensitive resin film obtained in the above (2) is heat-treated at 230 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film B.
(4) In the IR spectrum of the photosensitive resin film obtained in the above (1), the peak height near 910 cm ⁻¹ derived from the epoxy group is defined as _PO, and the cured film A obtained in the above (3) is obtained. in IR spectrum, the peak height in the vicinity of 910 cm ^-1 derived from the epoxy group and _{P a,} the IR spectrum of the cured film B, when the peak height in the vicinity of 910 cm ^-1 derived from the epoxy group was _{P B,} cure rate at 170 ° C. (%) of the _{formula: -} calculating on the basis of [1 ((P a -P B ) / (P O -P B))] × 100.

  The photosensitive resin composition of the present embodiment is obtained by subjecting a cured film (test sample) obtained by heat treatment at 170 ° C. for 180 minutes in a nitrogen atmosphere to a planar direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. ) Has an upper limit of, for example, 200 ppm / ° C. or less, preferably 190 ppm / ° C. or less, and more preferably 180 ppm / ° C. or less. Thereby, the film characteristics at the time of low-temperature curing can be improved, and the heat resistance can be improved. The lower limit of the average linear expansion coefficient (α2) is not particularly limited, but may be 80 ppm / ° C. or more, or 90 ppm / ° C. or more.

  Next, the semiconductor device and the electronic device of the present embodiment will be described.

  FIG. 1 is a longitudinal sectional view showing an example of the semiconductor device of the present embodiment. FIG. 2 is a partially enlarged view of a region surrounded by a chain line in 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 semiconductor 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 thereon.

  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. A lower wiring layer 24, an upper wiring layer 25 provided on the upper surface of the insulating layer 21, and a solder bump 26 provided on the lower surface of the lower wiring layer 24.

  The semiconductor package 3 includes a package substrate 31, a semiconductor chip 32 mounted on the package substrate 31, bonding wires 33 for electrically connecting the semiconductor chip 32 and the package substrate 31, and a semiconductor chip 32 and a bonding wire 33. The package includes a buried sealing layer and a solder bump provided on the lower surface of the package substrate.

  The semiconductor package 3 is stacked on the through electrode substrate 2. Thus, the solder bump 35 of the semiconductor package 3 and the upper wiring layer 25 of the through electrode substrate 2 are electrically connected.

  In such a semiconductor device 1, since it is not necessary to use a thick substrate such as an organic substrate including a core layer in the through electrode substrate 2, the height can be easily reduced. For this reason, it is possible to contribute to downsizing of an electronic device incorporating the semiconductor device 1.

  Further, since the through-electrode substrate 2 having different semiconductor chips and the semiconductor package 3 are stacked, the mounting density per unit area can be increased. For this reason, both miniaturization and high performance can be achieved.

Hereinafter, the through electrode substrate 2 and the semiconductor package 3 will be described in more detail.
The lower wiring layer 24 and the upper wiring layer 25 included in the through electrode substrate 2 shown in FIG. 2 each include an insulating layer, a wiring layer, a through wiring, and the like. As a result, the lower wiring layer 24 and the upper wiring layer 25 include wiring inside and 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 redistribution layer of the semiconductor chip 23, and the solder bumps 26 function as external terminals of the semiconductor chip 23.

  The through wiring 221 shown in FIG. 2 is provided so as to penetrate the insulating layer 21 as described above. As a result, the lower wiring layer 24 and the upper wiring layer 25 are electrically connected to each other, and the through-electrode substrate 2 and the semiconductor package 3 can be stacked. Therefore, the functionality of the semiconductor 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 functions 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 for forming an insulating layer of a rewiring layer.

  According to the present embodiment, the semiconductor device includes the semiconductor chip 23 and the redistribution layer (the upper wiring layer 25) provided on the surface of the semiconductor chip 23, and the insulating layer in the redistribution layer is used in the present embodiment. Semiconductor device composed of a cured product of the photosensitive resin composition of the present invention.

  Since the through wiring 221 penetrates the insulating layer 21, an effect of reinforcing the insulating layer 21 is obtained. For this reason, even when the mechanical strength of the lower wiring layer 24 and the upper wiring layer 25 is low, a decrease in the mechanical strength of the entire through electrode substrate 2 can be avoided. As a result, the lower wiring layer 24 and the upper wiring layer 25 can be further thinned, and the height of the semiconductor device 1 can be further reduced.

  The semiconductor 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, in addition to the through wiring 221. Thus, electrical connection between the upper surface of the semiconductor chip 23 and the upper wiring layer 25 can be achieved.

  The insulating layer 21 is provided so as to cover the semiconductor chip 23. Thereby, the effect of protecting the semiconductor chip 23 is enhanced. As a result, the reliability of the semiconductor device 1 can be improved. Further, the semiconductor device 1 that can be easily applied to a mounting method such as the package-on-package structure according to the present embodiment is 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. Thereby, the conductivity of the through wiring 221 can be ensured without impairing the mechanical characteristics of the insulating layer 21.

  The semiconductor package 3 shown in FIG. 1 may be any type of package. For example, QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip Size Package), QFN (Quad Flat Non-logged, Long-packed, Long-packed, Long-packed, Long-packed, Long-packed, Long-packed, Long-packed, Long-packed) Examples include LF-BGA (Lead Frame BGA).

  The arrangement of the semiconductor chips 32 is not particularly limited. For example, in FIG. 1, a plurality of semiconductor chips 32 are stacked. Thereby, the packing density is increased. The plurality of semiconductor chips 32 may be provided side by side in the plane direction, or may be provided in the plane direction while being stacked in the thickness direction.

  The package substrate 31 may be any substrate. For example, the package substrate 31 is a substrate including an insulating layer (not shown), a wiring layer, a through wiring, and the like. Among 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 wires 33 can be protected from external force and external environment.

  Since 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, it is possible to enjoy advantages such as high speed and low loss of mutual communication. Can be. From this viewpoint, for example, one of the semiconductor chip 23 and the semiconductor chip 32 is 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 Random Access). Memory, a memory element such as a flash memory, or the like, these elements can be arranged close to each other in the same device. As a result, the semiconductor device 1 that achieves both high functionality and miniaturization can be realized.

<Semiconductor device manufacturing method>
Next, a method of manufacturing the semiconductor device 1 shown in FIG. 1 will be described.

  FIG. 3 is a process chart showing a method for manufacturing the semiconductor device 1 shown in FIG. 4 to 6 are views for explaining a method of manufacturing the semiconductor device 1 shown in FIG.

  The method for manufacturing the semiconductor device 1 includes a chip disposing step S1 for obtaining the insulating layer 21 so as to bury the semiconductor chip 23 and the through wirings 221 and 222 provided on the substrate 202, and an upper layer on the insulating layer 21 and the semiconductor chip 23. An upper wiring layer forming step S2 for forming the wiring layer 25; a substrate peeling step S3 for peeling the substrate 202; a lower wiring layer forming step S4 for forming the lower wiring layer 24; 2 and a lamination step S6 of laminating the semiconductor package 3 on the through electrode substrate 2.

  Among them, the upper wiring layer forming step S2 is to dispose the photosensitive resin varnish 5 (varnish-like photosensitive resin composition) on the insulating layer 21 and the semiconductor chip 23 to obtain the first resin A film disposing step S20, a first exposing step S21 for exposing the photosensitive resin layer 2510 to an exposure treatment, a first developing step S22 for exposing the photosensitive resin layer 2510 to a development treatment, and a curing treatment to the photosensitive resin layer 2510. A first curing step S23, a wiring layer forming step S24 for forming the wiring layer 253, and a second resin for disposing the photosensitive resin varnish 5 on the photosensitive resin layer 2510 and the wiring layer 253 to obtain the photosensitive resin layer 2520 A film disposing step S25, a second exposing step S26 for performing an exposure process on the photosensitive resin layer 2520, a second developing step S27 for performing a developing process on the photosensitive resin layer 2520, and a photosensitive resin layer 2520. It includes a second curing step S28 is subjected to a curing treatment, a through wiring formation step S29 of forming the through wiring 254 to the opening 424 (the through hole), the.

  Hereinafter, each step will be sequentially described. The following manufacturing method is an example, and the present invention is not limited to this.

[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. An 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 bonded on the substrate 202. In the present manufacturing method, as an example, a plurality of semiconductor chips 23 are provided 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 types. Further, the space between the substrate 202 and the semiconductor chip 23 may be fixed via an adhesive layer (not shown) such as a die attach film.

  Note that an interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23 as necessary. The interposer functions as a redistribution layer of the semiconductor chip 23, for example. Therefore, the interposer may include a pad (not shown) for electrically connecting to an electrode of the semiconductor chip 23 described later. Thereby, the pad spacing and arrangement pattern of the semiconductor chip 23 can be converted, and the degree of freedom in designing the semiconductor device 1 can be further increased.

  As such an interposer, for example, an inorganic substrate such as a silicon substrate, a ceramic substrate, and a glass substrate, and an organic substrate such as a resin substrate are used.

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

  Examples of the constituent material of the through wirings 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.

  In addition, you may make it prepare the chip embedding structure 27 manufactured by the method different from the above.

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

[2-1] First resin film disposing step S20
First, as shown in FIG. 4B, the photosensitive resin varnish 5 is applied (disposed) on the insulating layer 21 and the semiconductor chip 23. Thus, a liquid coating of the photosensitive resin varnish 5 is obtained as shown in FIG. The photosensitive resin varnish 5 is a photosensitive resin composition of the present embodiment, and is a varnish having photosensitivity.

  The application of the photosensitive resin varnish 5 is performed using, for example, a spin coater, a bar coater, a spray device, an ink jet 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 semiconductor 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 viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 100 rpm.

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

  The drying conditions of the photosensitive resin varnish 5 are not particularly limited, and include, for example, 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 a photosensitive resin film formed by forming the photosensitive resin varnish 5 into a film may be adopted. The photosensitive resin film is a photosensitive resin composition of the present embodiment, and is a resin film having photosensitivity.

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

  After forming the photosensitive resin layer 2510 in this manner, a pre-exposure bake is performed on the photosensitive resin layer 2510 as necessary. By performing the pre-exposure bake 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 heating conditions as described below, adverse effects on the photoacid generator due to heating can be minimized.

  The temperature of the pre-exposure bake is preferably from 70 to 130C, more preferably from 75 to 120C, and even more preferably from 80 to 110C. If the temperature of the pre-exposure bake is below the lower limit, the purpose of stabilizing molecules by the pre-exposure bake may not be achieved. On the other hand, if the temperature of the pre-exposure bake exceeds the upper limit, the movement of the photoacid generator becomes too active, and the acid is hardly generated even when irradiated with light in a first exposure step S21 described later. May be widened and patterning processing accuracy may be reduced.

  The time of the pre-exposure bake is appropriately set according to the temperature of the pre-exposure bake, but is preferably 1 to 10 minutes, more preferably 2 to 8 minutes at the above-mentioned temperature, and still more preferably Allow 3-6 minutes. If the time of the pre-exposure bake is below the lower limit, the heating time is insufficient, and the purpose of stabilizing molecules by the pre-exposure bake may not be achieved. On the other hand, when the time of the pre-exposure baking exceeds the upper limit, the heating time is too long, so that even if the temperature of the pre-exposure baking is within the above range, the action of the photoacid generator is hindered. There is a possibility that it will.

  The atmosphere for the heat treatment is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like.

  In addition, the atmospheric pressure is not particularly limited, and may be under reduced pressure or under increased pressure. Note that the normal pressure refers to a pressure of about 30 to 150 kPa, and is preferably atmospheric pressure.

[2-2] First exposure step S21
Next, exposure processing is performed on the photosensitive resin layer 2510.

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

  Note that FIG. 4D illustrates a case where the photosensitive resin layer 2510 has a so-called negative-type photosensitivity. In this example, in the photosensitive resin layer 2510, a region corresponding to the light shielding portion of the mask 412 is provided with solubility in the developing solution.

  On the other hand, in a region corresponding to the transmission part of the mask 412, for example, an acid is generated by the action of the photosensitive agent. The generated acid acts as a catalyst for the reaction of the thermosetting resin in a step described later.

The exposure amount in the exposure treatment is not particularly limited, but is preferably 100 to 2000 mJ / cm ^2, and more preferably 200~1000mJ / cm ^2. Thus, underexposure and overexposure of the photosensitive resin layer 2510 can be suppressed. As a result, high patterning accuracy can be finally achieved.
Thereafter, if necessary, the photosensitive resin layer 2510 is subjected to a post-exposure bake treatment.

  The temperature of the post-exposure bake is not particularly limited, but is preferably 50 to 150C, more preferably 50 to 130C, still more preferably 55 to 120C, and particularly preferably 60 to 110C. Is done. By performing post-exposure bake at such a temperature, the catalytic action of the generated acid is sufficiently enhanced, and the thermosetting resin can be reacted in a shorter time and sufficiently. By setting the temperature within the above range, it is possible to suppress a decrease in patterning processing accuracy due to promotion of acid diffusion.

  Note that by setting the temperature of the post-exposure bake treatment equal to or higher than the lower limit, 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 bake treatment to be equal to or lower than the above upper limit, it is possible to suppress a reduction in patterning processing accuracy due to promotion of acid diffusion.

  On the other hand, the time of the post-exposure bake is appropriately set in accordance with the temperature of the post-exposure bake, but is preferably 1 to 30 minutes, more preferably 2 to 20 minutes, more preferably 2 to 20 minutes at the above-mentioned temperature. 3 to 15 minutes. By performing the post-exposure bake treatment for such a period of time, the thermosetting resin can be sufficiently reacted, and the diffusion of acid can be suppressed to suppress a reduction in patterning processing accuracy.

  The atmosphere for the post-exposure bake is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like.

  Further, the atmospheric pressure of the post-exposure bake is not particularly limited, and may be under reduced pressure or under increased pressure. Thereby, the pre-exposure baking can be performed relatively easily. Note that the normal pressure refers to a pressure of about 30 to 150 kPa, and is preferably atmospheric pressure.

[2-3] First Development Step S22
Next, the photosensitive resin layer 2510 is subjected to development processing. Thus, an opening 423 penetrating the photosensitive resin layer 2510 is formed in a region corresponding to the light-shielding portion of the mask 412 (see FIG. 5E).
Examples of the developer include an organic developer and a water-soluble developer.

[2-4] First curing step S23
After the development, the photosensitive resin layer 2510 is subjected to a curing treatment (a post-development heat treatment). The conditions for the curing treatment are not particularly limited, and the heating temperature is about 160 to 250 ° C. and the heating time is about 30 to 240 minutes. This makes it possible to cure the photosensitive resin layer 2510 while suppressing the thermal influence on the semiconductor chip 23, and obtain the organic insulating layer 251.

[2-5] Wiring layer forming step S24
Next, a wiring layer 253 is formed over the organic insulating layer 251 (see FIG. 5F). The wiring layer 253 is formed by obtaining a metal layer using a vapor deposition method such as a sputtering method or a vacuum evaporation method, and then patterning the metal layer by a photolithography method and an etching method.

  Note that a surface modification treatment such as a plasma treatment may be performed before the formation of the wiring layer 253.

[2-6] Second resin film disposing step S25
Next, as shown in FIG. 5G, a photosensitive resin layer 2520 is obtained in the same manner as in the first resin film disposing step S20. The photosensitive resin layer 2520 is disposed so as to cover the wiring layer 253.

  Thereafter, if necessary, the photosensitive resin layer 2520 is subjected to a heat treatment before exposure. The processing conditions are, for example, the conditions described in the first resin film disposing step S20.

[2-7] Second exposure step S26
Next, exposure processing is performed on the photosensitive resin layer 2520. The processing conditions are, for example, the conditions described in the first exposure step S21.

  After that, a post-exposure bake is performed on the photosensitive resin layer 2520 as necessary. 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 development processing. The processing conditions are, for example, the conditions described in the first developing step S22. Thus, an opening 424 penetrating the photosensitive resin layers 2510 and 2520 is formed (see FIG. 5H).

[2-9] Second curing step S28
After the development processing, the photosensitive resin layer 2520 is subjected to a curing processing (a heat treatment after the development). The curing conditions are, for example, the conditions described in the first curing step S23. Thereby, the photosensitive resin layer 2520 is cured, and the organic insulating layer 252 is obtained (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-line forming step S29
Next, a through wiring 254 shown in FIG. 6I is formed in the opening 424.

  A known method is used for forming the through wiring 254, 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. The seed layer is formed by, for example, a sputtering method.

  Further, the seed layer may be made of the same metal as the through wiring 254 to be formed, or may be made of a different metal.

  Next, a resist layer (not shown) is formed on a region other than the opening 424 of the seed layer (not shown). Then, the opening 424 is filled with metal using the resist layer as a mask. 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, and the through wiring 254 is formed.

Next, the 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 illustrated position.

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

[4] Lower wiring layer forming step S4
Next, as shown in FIG. 6K, a lower wiring layer 24 is formed on the lower surface side of the insulating layer 21. The lower wiring layer 24 may be formed by any method. For example, the lower wiring layer 24 may be formed in the same manner as in the above-described upper wiring layer forming step S2.

  The lower wiring layer 24 thus formed is electrically connected to the upper wiring layer 25 via the through wiring 221.

[5] Solder bump forming step S5
Next, as shown in FIG. 6L, 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 as necessary.
As described above, the through electrode substrate 2 is obtained.

  Note that the through electrode substrate 2 shown in FIG. 6L can be divided into a plurality of regions. Therefore, for example, by dividing the through-electrode substrate 2 along the dashed line shown in FIG. 6 (L), a plurality of through-electrode substrates 2 can be efficiently manufactured. In addition, for example, a diamond cutter or the like can be used for singulation.

[6] Lamination step S6
Next, the semiconductor package 3 is disposed on the singulated through electrode substrate 2. Thereby, the semiconductor device 1 shown in FIG. 1 is obtained.

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

<Modification of Semiconductor Device>
Next, a modified example of the semiconductor device according to the embodiment will be described.

(First Modification)
First, a first modified example will be described.
FIG. 7 is a partially enlarged cross-sectional view illustrating a first modification of the semiconductor device according to the embodiment.
Hereinafter, a first modified example will be described. In the following description, differences from the embodiment shown in FIGS. 1 and 2 will be mainly described, and a description of the same matters will be omitted. 1 and 2 are denoted by the same reference numerals in FIG.

  The semiconductor device 1A shown in FIG. 7 is the same as the semiconductor device 1 shown in FIGS. 1 and 2 except that the structure of the lower wiring layer is different. That is, the semiconductor device 1A shown in FIG. 7 includes the semiconductor chip 23 on which the lands 231 are provided, the lower wiring layer 24A, and the solder bumps 26. The structure of the lower wiring layer 24A is different from the structure of the lower wiring layer 24 shown in FIGS.

  Specifically, the lower wiring layer 24A shown in FIG. 7 includes an organic insulating layer 240 provided on the lower surface of the semiconductor chip 23, and an organic insulating layer 241 provided below the organic insulating layer 240. . At least one of the organic insulating layers 240 and 241 is formed using a photosensitive resin composition for a bump protective film. The lower surface of the semiconductor chip 23 is covered with the organic insulating layers 240 and 241.

  Further, the lower wiring layer 24A shown in FIG. 7 includes a bump adhesion layer 245 that is electrically connected to both the land 231 and the solder bump 26.

  By using the photosensitive resin composition for a bump protective film in the manufacture of such a first modification, patterning accuracy is high, and deterioration of the metal contained in the land 231 and the bump adhesion layer 245 can be suppressed. Therefore, a highly reliable semiconductor device 1A is obtained.

(Second Modification)
Next, a second modified example will be described.
FIG. 8 is a partially enlarged cross-sectional view illustrating a second modification of the semiconductor device according to the embodiment.
Hereinafter, a second modified example will be described, but in the following description, differences from the embodiment shown in FIGS. 1 and 2 will be mainly described, and description of the same items will be omitted. In addition, about the structure similar to FIG. 1, 2, the same code | symbol is attached | subjected in FIG.

  The semiconductor device 1B shown in FIG. 8 is the same as the semiconductor device 1 shown in FIGS. 1 and 2 except that the structure of the lower wiring layer is different. That is, the semiconductor device 1B shown in FIG. 8 includes the semiconductor chip 23 on which the lands 231 are provided, the lower wiring layer 24B, and the solder bumps 26. The structure of the lower wiring layer 24B is different from the structure of the lower wiring layer 24 shown in FIGS.

  Specifically, the lower wiring layer 24B shown in FIG. 8 includes an organic insulating layer 240 provided on the lower surface of the semiconductor chip 23, an organic insulating layer 241 provided below the organic insulating layer 240, and an organic insulating layer 241. , An organic insulating layer 242 provided below. At least one of these organic insulating layers 240, 241, 242 is formed using a photosensitive resin composition for a bump protective film.

  The lower wiring layer 24B shown in FIG. 8 includes a wiring layer 243 electrically connected to the land 231; a bump adhesion layer 245 electrically connected to both the wiring layer 243 and the solder bump 26; It has. The organic insulating layers 240 and 241 are interposed between the semiconductor chip 23 and the wiring layer 243, and the lower surface of the wiring layer 243 is covered with the organic insulating layer 242.

  In the manufacture of such a second modification, by using the photosensitive resin composition for a bump protective film, the patterning accuracy is high, and the deterioration of the metal contained in the lands 231, the wiring layers 243, and the bump adhesion layers 245 is suppressed. be able to. Therefore, a highly reliable semiconductor device 1B is obtained.

<Electronic device>
The electronic device according to the present embodiment includes the above-described semiconductor device according to the present embodiment.

  The electronic device according to the present embodiment is not particularly limited as long as it includes such a semiconductor device.For example, mobile phones, smartphones, tablet terminals, wearable terminals, information devices such as personal computers, servers, and routers Industrial equipments such as communication devices, robots and machine tools, vehicle control computers, and in-vehicle devices such as car navigation systems.

  Although the present invention has been described based on the illustrated embodiments, the present invention is not limited to these embodiments.

  For example, the method of manufacturing a semiconductor device according to the present invention may be a method in which an optional step is added to the above embodiment.

  Further, the photosensitive resin composition, the semiconductor device, and the electronic device of the present invention may be obtained by adding arbitrary elements to the above embodiment.

  Further, the photosensitive resin composition is applied not only to semiconductor devices but also to bump protection films of MEMS (Micro Electro Mechanical Systems) and various sensors, bump protection films of liquid crystal display devices, display devices such as organic EL devices, and the like. It is possible.

  Further, the form of the package of the semiconductor device is not limited to the illustrated form, but may be any form.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

(Preparation of negative photosensitive resin composition)
The raw materials of the components blended according to Table 1 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain a mixed solution. Thereafter, the mixed solution was filtered through a 0.2 μm polypropylene filter to obtain a varnish-like photosensitive resin composition having a viscosity of about 100 cP at 25 ° C. The viscosity of the photosensitive resin composition was measured using a cone-plate viscometer (TV-25, manufactured by Toki Sangyo) at a rotational speed of 100 rpm.

The details of the raw materials of each component in Table 1 are as follows.
(Epoxy resin)
Epoxy resin 1: Epoxy resin 1: Multifunctional epoxy resin represented by the following structure (EPPN201, phenol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd., solid at 25 ° C., n = about 5)

(Phenoxy resin)
Phenoxy resin 1: bisphenol A type phenoxy resin (jER1256, manufactured by Mitsubishi Chemical Corporation, Mw: about 50,000)

(Photoacid generator)
-Photoacid generator 1: triarylsulfonium borate salt (CPI-310B, manufactured by San Apro)

(Thermal acid generator)
-Thermal acid generator 1: borate type sulfonium salt represented by the following structure (manufactured by Sanshin Chemical Co., Ltd., San-Aid SI-B3)

(Surfactant)
-Surfactant 1: Fluorine-containing and lipophilic group-containing oligomer (R-41, manufactured by DIC)

（溶剤）
・溶剤１：プロピルグリコールモノメチルエーテルアセテート（ＰＧＭＥＡ） (Silane coupling agent)
-Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane represented by the following chemical formula (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(solvent)
-Solvent 1: propyl glycol monomethyl ether acetate (PGMEA)

  The obtained photosensitive resin composition was evaluated based on the following evaluation items.

<Curing rate at 170 ° C>
(1) The obtained negative photosensitive resin composition is applied on a silicon wafer having a diameter of 8 inches so as to have a thickness of 8 μm after drying by spin coating, and dried at 100 ° C. for 3 minutes in the air. Thus, a photosensitive resin film was formed.
(2) The photosensitive resin film obtained in the above (1) is entirely exposed at 600 mJ / cm ² using an i-line stepper. Subsequently, the film was heated after exposure at 70 ° C. for 5 minutes in the air using a hot plate.
(3) The photosensitive resin film obtained in (2) was heated at 170 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film A. The photosensitive resin film obtained in the above (2) was subjected to a heat treatment at 230 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film B.
(4) The IR spectrum of the photosensitive resin film obtained in the above (1) was measured using Fourier transform infrared spectroscopy (FT-IR), and the peak height around 910 cm ⁻¹ derived from the epoxy group was measured. was a _{P O} is, in the IR spectrum of the cured film a obtained in the above (3), the peak height in the vicinity of 910 cm ^-1 derived from the epoxy group and _{P a,} the IR spectrum of the cured film B, epoxy group when the peak height in the vicinity of 910 cm ^-1 derived was _{P B,} the curing rate at 170 ° C. (%) of the _{formula: [1 - ((P a} -P B) / (P O -P B)) ] × 100. Table 1 shows the results.

<CTE>
The obtained negative photosensitive resin composition was heated at 170 ° C. for 180 minutes under a nitrogen atmosphere to obtain a cured sample film. Using a TMA (Thermal Mechanical Analyzer) test device (manufactured by Seiko Instruments Inc., product number: EXSTAR6000 TMA / SS6100), the obtained sample cured film was heated at a rate of 5 ° C./min, a load of 30 N, a tensile mode, Measurement range: Two cycles of thermomechanical analysis (TMA) were performed under the conditions of 150 ° C to 250 ° C. From the obtained results, the average value of the linear expansion coefficient (α2) in the plane direction (XY directions) in the range of 150 ° C to 250 ° C was calculated. In addition, the value of the 2nd cycle was adopted as the linear expansion coefficient (ppm / ° C.). Table 1 shows the results.

<Sensitivity (Eop)>
(1) The obtained negative photosensitive resin composition is applied on a silicon wafer having a diameter of 8 inches so as to have a thickness of 8 μm after drying by spin coating, and dried at 100 ° C. for 3 minutes in the air. Thus, a photosensitive resin film was formed.
(2) the obtained photosensitive resin film in the above (1), using an i-line ^stepper, steps exposed at ^{20mJ / cm 2 ~1240mJ / cm 2} . Subsequently, the film was heated after exposure at 70 ° C. for 5 minutes in the air using a hot plate. Subsequently, using a spray developing machine, development was performed with PGMEA in the air for 20 seconds, and patterning was performed.
(3) The photosensitive resin film obtained in (2) was heated at 170 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film.
(4) Among the patterning of the photosensitive resin film obtained in the above (1), a cross section of a square via corresponding to a 7 μm mask is observed by SEM, and an exposure amount (mJ / cm) of 7 μm CD (Critical Dimension) is obtained. ² ) was defined as Eop.

<Reflow resistance>
(1) The obtained negative photosensitive resin composition was subjected to a heat treatment at 170 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured sample film A. Further, a sample cured film B was obtained by performing a heat treatment at 230 ° C. for 180 minutes in a nitrogen atmosphere. Each of the obtained sample cured films A and B was subjected to a heat treatment at 260 ° C. for 5 minutes 10 times in a nitrogen atmosphere.
(2) Each of the sample cured films A and B obtained in the above (1) was raised using a TMA (Thermal Mechanical Analyzer) test device (manufactured by Seiko Instruments Inc., product number: EXSTAR6000 TMA / SS6100). Two cycles of thermomechanical analysis (TMA) were performed under the conditions of a temperature rate of 5 ° C./min, a load of 30 N, a tensile mode, and a measurement range temperature of 150 ° C. to 250 ° C. From the obtained results, the average value of the linear expansion coefficient (α2) in the plane direction (XY directions) in the range of 150 ° C. to 250 ° C. was calculated, and the linear expansion coefficient (α2) of the sample cured film B after reflow was calculated. The case where the ratio of the coefficient of linear expansion (α2) of the cured sample film A after reflow was less than 10% was evaluated as ○, and the case where the ratio was 10% or more and less than 50% was evaluated as Δ.

  It was found that the negative photosensitive resin compositions of Examples 1 to 3 were superior to Comparative Example 1 in low-temperature curability, sensitivity, and reflow resistance. Such photosensitive resin compositions of Examples 1 to 3 are suitable as negative photosensitive resin compositions used for insulating films of wiring layers and the like.

REFERENCE SIGNS LIST 1 semiconductor device 1A semiconductor device 1B semiconductor device 2 through electrode substrate 3 semiconductor package 5 photosensitive resin varnish 21 insulating layer 23 semiconductor chip 24 lower wiring layer 24A lower wiring layer 24B lower wiring layer 25 upper wiring layer 26 solder bump 27 chip embedding Structure 31 Package substrate 32 Semiconductor chip 33 Bonding wire 34 Sealing layer 35 Solder bump 202 Substrate 221 Through wiring 222 Through wiring 231 Land 240 Organic insulating layer 241 Organic insulating layer 242 Organic insulating layer 243 Wiring layer 245 Bump adhesion layer 251 Organic insulation Layer 252 Organic insulating layer 253 Wiring layer 254 Through wiring 412 Mask 423 Opening 424 Opening 2510 Photosensitive resin layer 2520 Photosensitive resin layer S1 Chip disposing step S2 Upper wiring layer forming step S20 First resin film disposing step S21 First exposure Process S 2 First developing step S23 First curing step S24 Wiring layer forming step S25 Second resin film disposing step S26 Second exposing step S27 Second developing step S28 Second curing step S29 Through wiring forming step S3 Substrate peeling step S4 Lower wiring layer Forming step S5 Solder bump forming step S6 Stacking step W Diameter

Claims (12)

A negative photosensitive resin composition for film formation,
Epoxy resin,
Phenoxy resin,
A photoacid generator,
A thermal acid generator containing an aromatic sulfonium salt represented by the following general formula (1),
A negative photosensitive resin composition comprising:

(In the general formula (1),
R ¹ represents any ^one of a hydrogen atom, a methoxycarbonyl group, an acetyl group, and a benzoyl group;
R ² represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
R ³ represents an alkyl group having 1 to 4 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, or an α-naphthylmethyl group;
R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.
X represents any one of SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , (CF ₃ SO ₂ ) ₂ N, and B (C ₆ F ₅ ) ₄ . ) A negative photosensitive resin composition according to claim 1,
A negative photosensitive resin composition, wherein the thermal acid generator contains a sulfonium salt borate salt in which X in the above general formula (1) represents BF ₄ or B (C ₆ F ₅ ) ₄ . The negative photosensitive resin composition according to claim 1 or 2,
A negative photosensitive resin composition, wherein the content of the thermal acid generator is 0.1% by mass or more and 3% by mass or less based on 100% by mass of the epoxy resin. A negative photosensitive resin composition according to any one of claims 1 to 3,
A negative photosensitive resin composition, wherein the weight average molecular weight of the phenoxy resin is from 10,000 to 100,000. It is a negative photosensitive resin composition according to any one of claims 1 to 4,
A negative photosensitive resin composition having a curing rate of 170% or more at 170 ° C. measured by the following procedure.
(procedure)
(1) The negative photosensitive resin composition is applied on a silicon wafer having a diameter of 8 inches by spin coating so that the film thickness becomes 8 μm after drying, and dried in air at 100 ° C. for 3 minutes. A photosensitive resin film is formed.
(2) The photosensitive resin film obtained in the above (1) is entirely exposed at 600 mJ / cm ² using an i-line stepper. Subsequently, the substrate is heated after exposure at 70 ° C. for 5 minutes in the air using a hot plate.
(3) The photosensitive resin film obtained in the above (2) is heated at 170 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film A. Further, the photosensitive resin film obtained in the above (2) is heat-treated at 230 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured film B.
(4) The IR spectrum of the photosensitive resin film obtained in the above (1) was measured by using Fourier transform infrared spectroscopy (FT-IR), and the peak height around 910 cm ⁻¹ derived from the epoxy group was measured. was a _{P O} is, in the IR spectrum of the cured film a obtained in the above (3), the peak height in the vicinity of 910 cm ^-1 derived from the epoxy group and _{P a,} the IR spectrum of the cured film B, epoxy group when the peak height in the vicinity of 910 cm ^-1 derived was _{P B,} the curing rate at 170 ° C. (%) of the _{formula: [1 - ((P a} -P B) / (P O -P B)) ] × 100. It is a negative photosensitive resin composition according to any one of claims 1 to 5,
The average linear thermal expansion coefficient (α2) in the planar direction of the cured film obtained by subjecting the negative photosensitive resin composition to heat treatment at 170 ° C. for 180 minutes in a nitrogen atmosphere, calculated from 150 ° C. to 250 ° C. Is 200 ppm / ° C. or less, a negative photosensitive resin composition. A negative photosensitive resin composition according to any one of claims 1 to 6,
A negative photosensitive resin composition containing a surfactant. It is a negative photosensitive resin composition according to any one of claims 1 to 7,
A negative photosensitive resin composition containing an adhesion aid. A negative photosensitive resin composition according to any one of claims 1 to 8,
A negative photosensitive resin composition containing a solvent. It is a negative photosensitive resin composition according to any one of claims 1 to 9,
A negative photosensitive resin composition, wherein the viscosity at 25 ° C. of the negative photosensitive resin composition is 10 cP or more and 6000 cP or less. A negative photosensitive resin composition according to any one of claims 1 to 10,
A negative photosensitive resin composition, wherein the cured film of the negative photosensitive resin composition is used to form an insulating layer of a rewiring layer. A semiconductor chip,
A redistribution layer provided on the surface of the semiconductor chip,
A semiconductor device, wherein the insulating layer in the redistribution layer is made of a cured product of the negative photosensitive resin composition according to claim 1.

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