WO2017111057A1

WO2017111057A1 - Sealant for semiconductor

Info

Publication number: WO2017111057A1
Application number: PCT/JP2016/088444
Authority: WO
Inventors: 完二田; 佐藤　和也
Original assignee: 太陽インキ製造株式会社
Priority date: 2015-12-25
Filing date: 2016-12-22
Publication date: 2017-06-29
Also published as: JP2017118045A; PH12018501308A1; TWI750145B; MY196462A; CN108369928A; KR102384582B1; JP5978380B1; KR20180098558A; CN108369928B; TW201737429A

Abstract

Provided is a sealant for semiconductor whereby it is possible to inhibit the formation of a gap between a semiconductor chip and the sealant for semiconductor. The sealant for semiconductor according to the present invention is characterized by containing an oxidizing agent capable of oxidizing a semiconductor.

Description

Sealant for semiconductor

The present invention relates to a semiconductor sealing material for protecting a semiconductor chip, and more particularly to a semiconductor used in a fan-out type wafer level package in which an arrangement area of an external connection electrode is larger than a semiconductor planar size. It relates to a sealing material.

In recent years, there has been an increasing demand for miniaturization in the field of semiconductor circuits and the like, and in order to meet the demands, semiconductor circuits may be mounted in a package (Chip Size Package) close to the chip size. As one of means for realizing a chip size package, a packaging method called a wafer level package (hereinafter, sometimes abbreviated as WLP) that is bonded and fragmented at a wafer level has been proposed. WLP is attracting attention because it can contribute to cost reduction and size reduction. The WLP is mounted face down on a circuit board on which electrodes are formed.

By the way, with the miniaturization and high integration of the semiconductor chip, the number of electrodes (terminals and bumps) for external connection of the semiconductor chip tends to increase. Therefore, the pitch of the electrodes for external connection of the semiconductor chip is small. Tend to be. However, it is not always easy to directly mount a semiconductor chip on which bumps are formed at a fine pitch on a circuit board.

In order to solve the above problems, a semiconductor encapsulant region is formed on the outer periphery of the semiconductor chip, and a rewiring layer connected to the electrode is also provided in the semiconductor encapsulant region, so that the bump pitch is reduced. It has been proposed to be larger. Such a WLP is called a fan-out type wafer level package (hereinafter sometimes abbreviated as FO-WLP) because the size of the bump arrangement area is larger than the size of the semiconductor chip.

In FO-WLP, a semiconductor chip is embedded with a semiconductor sealing material. The circuit surface of the semiconductor chip is exposed to the outside, and a boundary between the semiconductor chip and the semiconductor sealing material is formed. A rewiring layer connected to the electrode of the semiconductor chip is also provided in the region of the semiconductor sealing material for embedding the semiconductor chip, and the bump is electrically connected to the electrode of the semiconductor chip through the rewiring layer. The pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.

It is also conceivable that not only a semiconductor chip but also a plurality of electronic components are contained in one package, or a plurality of semiconductor chips are embedded in a semiconductor sealing material to form one semiconductor component. In such a package, a plurality of electronic components are embedded with a semiconductor sealing material. The semiconductor sealing material for embedding a plurality of electronic components is provided with a rewiring layer connected to the electrodes of the electronic components, and the bumps are electrically connected to the electrodes of the electronic components via the rewiring layers. Also in this case, it can be said that FO-WLP because the size of the bump arrangement area is larger than the size of the semiconductor chip.

In such a package, in general, a semiconductor chip or an electronic component is arranged at a certain interval on a support, embedded with a semiconductor sealing material, and the sealing material is heat-cured, and then the support. A pseudo wafer is produced by peeling from the substrate. Subsequently, a rewiring layer is formed from the semiconductor chip circuit surface of the pseudo wafer to the expanded semiconductor sealing material region. In this way, the pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.

In the formation of the rewiring layer, generally, a positive sensitive resin is applied to the semiconductor chip circuit surface of the pseudo wafer, prebaked, and activated with UV light or the like in an area to be opened through a photomask or the like. Irradiate light, then develop using a developer such as TMAH (tetramethylammonium hydroxide), heat cure, oxygen plasma treatment, etc., metal electrode sputtering, and further form a photoresist layer The wiring is patterned to form a rewiring layer (for example, Patent Document 1).

JP 2013-38270 A

However, when FO-WLP is manufactured through the above-described steps, a gap is generated at the boundary between the semiconductor chip and the semiconductor sealing material, and the reliability of the rewiring layer formed thereafter is reduced. There was a problem. In addition, this gap has a problem of reducing the product reliability of the completed FO-WLP.

Therefore, an object of the present invention is to provide a semiconductor sealing material, particularly a FO-WLP sealing material, which can suppress the formation of a gap between the semiconductor chip and the semiconductor sealing material.

The present inventors have studied in detail the phenomenon that the boundary between the semiconductor chip and the semiconductor sealing material is generated, and it is found that this gap is generated in the development process used when the rewiring layer is formed. I found it. Then, further investigation was made, and during the development process, the developer also entered the boundary of the side surface of the semiconductor chip embedded in the semiconductor encapsulant, and in some cases, the semiconductor encapsulant soaked. It has been found that a gap is generated at the boundary between the side surface of the semiconductor chip and the semiconductor sealing material by etching the side surface of the semiconductor chip with the developer that has entered or has penetrated.

As a result of intensive studies based on the above findings, the present inventors have added a component that prevents the semiconductor wafer from being etched by the developer to the semiconductor encapsulant, thereby forming the rewiring layer. Even when a developing solution is used, it is possible to suppress the formation of a gap at the boundary between the side surface of the semiconductor chip and the semiconductor sealing material. As a result, the rewiring layer can be easily formed and the reliability of the completed FO-WLP It was found that can be improved.

The semiconductor sealing material according to the present invention is characterized by comprising an oxidizing agent capable of oxidizing a semiconductor.

In the embodiment of the present invention, the semiconductor sealing material may contain a curable component, a curing agent component, a curing accelerator component, and an inorganic filler.

In the aspect of the present invention, the semiconductor sealing material may have a sheet-like shape.

In the embodiment of the present invention, it may be used for a fan-out type wafer level package.

According to the semiconductor sealing material of the present invention, it is possible to suppress the formation of a gap between the semiconductor chip and the semiconductor sealing material, particularly in FO-WLP. As a result, the rewiring layer can be easily formed during the manufacture of the FO-WLP, and the reliability of the completed FO-WLP can be improved.

The semiconductor sealing material protects a semiconductor element (for example, a semiconductor chip) processed from a semiconductor wafer from heat and dust to form a semiconductor package, and seals and insulates the entire semiconductor element. It is. The semiconductor sealing material contains each component as a sealing material as described later, but the semiconductor sealing material according to the present invention is characterized by containing an oxidizing agent capable of oxidizing the semiconductor. Yes. As described above, for example, when manufacturing FO-WLP, a rewiring layer is formed on the semiconductor chip circuit surface of a pseudo wafer formed by embedding a semiconductor chip or the like with a semiconductor sealing material. When patterning the wiring layer, a developer such as TMAH is used. During the development processing, the developer enters the interface between the embedded semiconductor chip and the semiconductor sealing material. For example, in the case of a silicon semiconductor chip, silicon is etched by a TMAH developer, and a gap is generated between the embedded semiconductor wafer and the semiconductor sealing material. In the present invention, since the semiconductor encapsulant contains an oxidizing agent that can oxidize the semiconductor wafer, the surface of the semiconductor chip is oxidized when the semiconductor chip is encapsulated with the semiconductor encapsulant. For example, in the case of a silicon (Si) semiconductor chip, a very thin film of SiO ₂ is formed on the surface of the semiconductor chip. Therefore, even when the developer enters the interface between the semiconductor chip and the semiconductor sealing material during the subsequent development processing, the silicon semiconductor is prevented from being etched by the developer due to the oxide film (SiO ₂ ). Can be considered. This is only a guess of the present inventors, and the present invention is not bound to the logic.

Examples of a semiconductor chip sealed with a semiconductor sealing material include silicon (Si), germanium (Ge), SiGe, and the like, and a silicon semiconductor is generally used.

The oxidizing agent that can be used in the present invention is not particularly limited as long as it is an oxidizing agent capable of oxidizing the semiconductor as described above, and may be either an organic oxidizing agent or an inorganic oxidizing agent. However, from the viewpoint of compatibility with other components constituting the semiconductor sealing material described later, an organic oxidizing agent can be preferably used.

As the organic oxidizing agent, an organic oxidizing agent or an organic peroxide can be preferably used. Examples of the organic oxidizing agent include hydroperoxides, quinones, pyridines, and organic nitro compounds. Examples of the organic peroxide include m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, performic acid, benzoyl peroxide, diethyl peroxide, and diacetyl peroxide.

Hydroperoxides include t-butyl hydroxide, cumene hydroxide bis (trimethylsilyl) peroxide, ethyl hydroperoxide, tert-butyl hydroperoxide, succinic acid peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Is mentioned.

Examples of quinones include p-chloranil (tetrachloro-p-benzoquinone), o-chloranil, tetrabromo-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, chlorobenzoquinone, Examples include dichlorobenzoquinone, benzoquinone, naphthoquinone, anthraquinone, substituted anthraquinone, 2,3,5,6-tetrachloro-p-benzoquinone, and the like.

Examples of pyridines include pyridine oxide, pyridine N-oxide, dimethylaminopyridine oxide, 2,2,6,6, -tetramethyl-1-piperidinyl oxide, trimethylamine N-oxide and the like.

Examples of organic nitro compounds include metanitrobenzene sulfonate, paranitrobenzoate, nitroganidine, and aromatic nitrosulfonate.

Commercially available peroxides may also be used. For example, peroxyketals and perbutyl which are commercially available under the trade names of Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22 from Nippon Oil & Fats Co., Ltd. Hydroperoxides marketed under the trade names H, Parkmill H, Parkmill P, Permenta H, Perocta H, Peralkyl C, Perbutyl D, Dialkyl peroxides marketed under the trade name Perhexyl D, Parroyl IB, Products of diacyl peroxides, paroyl IPP, paroyl NPP, paroyl TCP, paroyl OPP, paroyl SBP marketed under the trade names of paroyl 355, paroyl L, paroyl SA, niper BW, niper BMT-K40, niper BMT-M Peroxydicarbonates, per mill ND, perocta ND, perhexyl ND, perbutyl ND, perhexyl PV, perbutyl PV, perhexa 25O, perocta O, perhexyl O, perbutyl O, perbutyl L, perbutyl 355, perhexyl I, Peroxyesters commercially available under the trade names of perbutyl I, perbutyl E, perhexa 25Z, perbutyl A, perhexyl Z, perbutyl ZT, perbutyl Z, other peromers AC, and BTTB-25 can be used.

The above oxidizing agents may be used alone or in combination of two or more.

In the present invention, among the oxidizing agents described above, from the viewpoint of both the reactivity with the semiconductor that forms an oxide layer on the surface of the semiconductor chip (oxidation) and the stability as a semiconductor sealing material. Organic peroxides and quinones are preferably used.

Examples of the inorganic oxidant include silver oxide, copper oxide, germanium oxide, indium oxide, manganese oxide, lead oxide, rhenium oxide, and tellurium oxide. Among these, manganese oxide and lead oxide are preferable from the balance of reactivity as an oxidizing agent and stability as a sealing material. Among the oxidizers described above, the organic oxidizer can be homogeneously mixed with the resin component of the semiconductor sealing material as compared with the inorganic oxidizer, and as a result, adheres to the surface of the semiconductor chip. By acting more homogeneously through the resin component, it is preferable because it is excellent in moisture resistance, and as a result, reliability such as suppression of gap formation is further improved.

The content of the oxidizing agent is preferably in the range of 0.01 to 10 parts by mass, with the total mass in terms of solid content of components other than the oxidizing agent being 100 parts by mass, 0.05 to 8 parts by mass. The range is more preferably in the range of 0.1 to 5 parts by mass. By setting the content of the oxidizing agent in the above range, formation of a gap on the side surface of the semiconductor chip can be suppressed without oxidizing and decomposing the semiconductor sealing material.

As described above, depending on the type of oxidizing agent, the resin component constituting the semiconductor sealing material may be oxidized. Therefore, in this invention, antioxidant may contain in the sealing material for semiconductors. Antioxidants include phenolic antioxidants and amine antioxidants that function as radical chain inhibitors, phosphorus antioxidants that function as peroxide decomposers, sulfur antioxidants, and metal deactivators. Hydrazine antioxidants, amide antioxidants, and the like that function as Among these, phenolic antioxidants and amine-based antioxidants can be preferably used. Commercially available antioxidants may also be used. For example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO -330, ADK STAB, PEP-36 / 36A, HP-10, 2112, 2112RG, PEP-8, PEP-8W, 1178, 1500, C, 135A, 3010, TPPADEKA stub AO-412S, AO-503, and the like.

When the antioxidant is contained in the semiconductor sealing material according to the present invention, the content thereof is 5 to 99 moles of the functional group of the antioxidant when the mole number of the functional group of the antioxidant is 100%. %, Preferably 8 to 90%, more preferably 10 to 80%. By keeping the content of the antioxidant in the above range, the reactivity of the oxidant with the semiconductor (oxidation) is maintained, and the reactivity of the oxidant is adjusted to suppress the oxidative decomposition of the resin component. Can do.

The semiconductor sealing material according to the present invention may contain a curable component, a curing agent component, a curing accelerator component, an inorganic filler, and the like as described later. Hereinafter, components other than the oxidizing agent and the antioxidant that constitute the semiconductor sealing material will be described.

<Curable component>
A conventionally known resin can be used as the curable component of the semiconductor sealing material without any particular limitation, but an epoxy resin is preferably used. Epoxy resins include solid, semi-solid, and liquid epoxy resins from the pre-reaction shape. These can be used individually by 1 type or in combination of 2 or more types. When an epoxy resin containing halogen is used, there is a risk of affecting the action of reducing the reactivity of the added oxidant, that is, suppressing the formation of gaps, due to the oxidation-reduction reaction between halide ions generated from hydrolysis and the oxidant. Therefore, it is preferable that the epoxy resin is halogen-free, and it is preferable that substantially no chlorine, bromine or iodine is contained among the halogens.

Specifically, the chlorine content in the epoxy resin is preferably 2500 ppm or less, the bromine content is 1000 ppm or less, and the total content of chlorine and bromine is 3000 ppm or less. The chlorine content is more preferably 2000 ppm or less, further preferably 1500 ppm or less, and particularly preferably 1000 ppm or less. Further, the sealing material is preferably halogen-free. Specifically, the chlorine content is preferably 900 ppm or less, the bromine content is 900 ppm or less, and the total content of chlorine and bromine is preferably 1500 ppm or less. In addition, as a measuring method of halogen content, it can measure by the flask combustion process ion chromatograph method based on a JPCA standard.

Solid epoxy resins include HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, and NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Naphthalene type epoxy resin such as EPPN-502H (Trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxy product of a condensate of phenols and aromatic aldehyde having a phenolic hydroxyl group (Trisphenol type epoxy resin); DIC Dicyclopentadiene aralkyl epoxy resin such as Epicron HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Type epoch Biphenyl / phenol novolac type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; Novolak type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX manufactured by Mitsubishi Chemical Corporation Biphenyl type epoxy resin such as −4000; phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co .; tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd., and the like.

Semi-solid epoxy resins include DIC's Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Toto Kasei Epoto YD-134, Mitsubishi Chemical Corporation jER834, jER872, Sumitomo Chemical Co., Ltd. Examples thereof include bisphenol A type epoxy resins such as ELA-134; naphthalene type epoxy resins such as Epicron HP-4032 manufactured by DIC; and phenol novolac type epoxy resins such as Epicron N-740 manufactured by DIC.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.

The above-mentioned curable components can be used alone or in combination of two or more. The compounding amount of the curable component is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the total solid content constituting the semiconductor sealing material. The blending amount of the liquid epoxy resin is preferably 0 to 45 parts by mass, more preferably 0 to 30 parts by mass, and 0 to 5 parts by mass with respect to 100 parts by mass of the curable component. It is particularly preferred. When the blending amount of the liquid epoxy resin is in the range of 0 to 45 parts by mass, the glass transition temperature (Tg) of the cured product is increased and crack resistance may be improved.

<Curing agent component>
A curing agent component may be included as a component constituting the semiconductor sealing material according to the present invention. The curing agent component has a functional group that reacts with the above-described curable component. Examples of such a curing agent component include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, and the like, and phenol resins are preferred. Among these, one kind can be used alone, or two or more kinds can be used in combination.

Examples of phenol resins include phenol novolac resins, alkylphenol volac resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins, polyvinylphenols, phenol / naphthol resins, Conventionally known ones such as an α-naphthol skeleton-containing phenol resin and a triazine-containing cresol novolak resin can be used singly or in combination of two or more.

The polycarboxylic acid and its acid anhydride are a compound having two or more carboxyl groups in one molecule and its acid anhydride, for example, a copolymer of (meth) acrylic acid, a copolymer of maleic anhydride, In addition to condensates of dibasic acids, resins having carboxylic acid ends such as carboxylic acid-terminated imide resins can be mentioned.

The cyanate ester resin is a compound having two or more cyanate ester groups (—OCN) in one molecule. Any conventionally known cyanate ester resins can be used. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. Is mentioned. Further, it may be a prepolymer partially triazine.

The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among these, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.

As the curing agent component, an alicyclic olefin polymer other than those described above can be used. As the alicyclic olefin polymer which can be suitably used, an alicyclic olefin having at least one of (1) a carboxyl group and a carboxylic anhydride group (hereinafter referred to as “carboxyl group etc.”) is necessary. (2) Aromatic ring portion of (co) polymer obtained by polymerizing aromatic olefin having carboxyl group or the like with other monomer as necessary (3) a copolymer of an alicyclic olefin having no carboxyl group and a monomer having a carboxyl group, (4) an aromatic olefin having no carboxyl group, A copolymer obtained by copolymerizing a monomer having a carboxyl group or the like with a hydrogenated aromatic ring part, and (5) a carbocyclic olefin polymer having no carboxyl group or the like. A compound in which a compound having a sil group or the like is introduced by a modification reaction, or (6) a carboxylic acid ester group of an alicyclic olefin polymer having a carboxylic acid ester group obtained as described in (1) to (5) above. Examples thereof include those converted into a carboxyl group by hydrolysis or the like.

Among the above curing agent components, phenol resin, cyanate ester resin, active ester resin, and alicyclic olefin polymer are preferable. In particular, it is more preferable to use a phenol resin because it has high polarity and easily suppresses the relative dielectric constant.

The curing agent component is a ratio of a functional group (functional group capable of curing reaction) such as an epoxy group of the curable component to a functional group of the curing agent component that can react with the functional group (the number of functional groups of the curing agent component). / The number of functional groups of the curable component: equivalent ratio) is preferably included in a ratio of 0.2 to 5. By setting the equivalent ratio in the above range, it is possible to obtain a semiconductor sealing material that is further excellent in protective properties.

<Curing accelerator component>
As a component constituting the semiconductor sealing material according to the present invention, a curing accelerator component may be included. The curing accelerator component promotes the curing reaction of the curable component, and can further improve the adhesion of the sealing material to the semiconductor wafer and the heat resistance. Curing accelerator components include imidazole and derivatives thereof; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide At least one of these organic acid salts and epoxy adducts; an amine complex of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino Triazine derivatives such as -6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) Amines such as melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, tri Organic phosphines such as phenylphosphine and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; benzyltrimethylammonium chloride and phenyltributylammonium chloride Quaternary ammonium salts such as the above; polybasic acid anhydrides; diphenyliodonium tetrafluoroboroates; Photocationic polymerization catalyst such as rusulfonium hexafluoroantimonate and 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate Conventionally known curing accelerators such as an equimolar reaction product of an organic polyisocyanate such as isophorone diisocyanate and dimethylamine, a metal catalyst, and the like can be used, and one of these can be used alone or in combination of two or more.

The curing accelerator component is not essential, but when it is desired to accelerate the curing reaction, it can be used preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the curable component described above. When a metal catalyst is used as the curing accelerator component, the content is preferably 10 to 550 ppm, more preferably 25 to 200 ppm in terms of metal with respect to 100 parts by mass of the curable component.

<Inorganic filler component>
The semiconductor sealing material according to the present invention may contain an inorganic filler component. By including the inorganic filler component, the reliability of the semiconductor sealing material is improved. Further, by applying laser marking to the back surface of the semiconductor sealing material, the inorganic filler component is exposed at the portion scraped off by the laser beam, and the reflected light diffuses to exhibit a color close to white. Thereby, when the sealing material for semiconductors contains the colorant component mentioned later, there is an effect that a contrast difference is obtained between the laser marking portion and other portions, and the marking (printing) becomes clear.

As the inorganic filler component, conventionally known ones can be used without limitation, for example, powders such as silica, alumina, talc, aluminum hydroxide, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like. Examples thereof include spheroidized beads, single crystal fibers, and glass fibers. One kind can be used alone, or two or more kinds can be mixed and used. Among these, silica, alumina, and titanium oxide are preferable.

The inorganic filler component preferably has an average particle size of 0.01 to 15 μm, more preferably 0.02 to 12 μm, particularly preferably 0.03 to 10 μm. In the present specification, the average particle size is the number average particle size calculated as the arithmetic average value of the major axis diameters of 20 inorganic filler components randomly selected with an electron microscope.

The content of the inorganic filler component is preferably 10 to 2000 parts by mass, more preferably 30 to 1800 parts by mass, and particularly preferably 60 to 1500 parts by mass with respect to 100 parts by mass of the total solid components constituting the semiconductor sealing material. Part.

<Colorant component>
The colorant component may be contained in the semiconductor sealing material according to the present invention. By including the colorant component, it is possible to prevent malfunction of the semiconductor device due to infrared rays or the like generated from surrounding devices when a semiconductor chip provided with a protective film is incorporated in the device. Further, when a protective film is engraved by means such as laser marking, marks such as characters and symbols can be easily recognized. That is, in a semiconductor chip on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off by laser light and printed). By containing, the contrast difference of the part scraped off with the laser beam of the protective film and the part which is not so is fully obtained, and visibility improves.

As the colorant component, organic or inorganic pigments and dyes can be used singly or in combination of two or more. Among these, black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties. Examples of the black pigment include carbon black, perylene black, iron oxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of preventing malfunction of the semiconductor device. Further, in place of carbon black, pigments such as red, blue, green, and yellow can be mixed to obtain black or a close black color.

The colorant component is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 25 parts by weight, and particularly preferably 1 to 15 parts by weight based on 100 parts by weight of the total solid content constituting the semiconductor sealing material. It is contained at a ratio of parts by mass.

<Coupling agent component>
A functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group in order to improve at least one of adhesion, adhesion, and cohesiveness of a protective film to an adherend (semiconductor wafer) of a semiconductor sealing material A coupling agent component having a group may be contained. Moreover, the water resistance can be improved without impairing the heat resistance of the protective film obtained by hardening | curing the sealing material for semiconductors by including a coupling agent component. Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.

Examples of organic groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, polysulfide groups, and isocyanate groups. Can be mentioned. Commercially available silane coupling agents can be used, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403. , KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM -573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; manufactured by Shin-Etsu Silicone) it can. These may be used alone or in combination of two or more.

<Film property imparting polymer component>
The semiconductor sealing material according to the present invention can be in the form of liquid, granule, sheet or the like. In this, when it is set as a sheet-like semiconductor sealing material, you may add the polymer component (film property provision polymer) which provides film formability. In the present specification, the film property-imparting polymer component means a polymer component having no reactive functional group in order to be distinguished from a reactive film property-imparting polymer component described later. Examples of such film-imparting polymer components include thermoplastic polyhydroxy polyether resins, phenoxy resins that are condensates of epichlorohydrin and various bifunctional phenol compounds, or hydroxyl groups in the hydroxy ether portion present in the skeleton, and various acid anhydrides. And phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, block copolymer and the like esterified using acid chloride. These polymers may be used alone or in combination of two or more. In order to maintain the film (or sheet) shape, the weight average molecular weight (Mw) of these polymers is usually 2 × 10 ⁴ or more, and preferably 2 × 10 ⁴ to 3 × 10 ⁶ .

In addition, in this specification, the value of a weight average molecular weight (Mw) can be measured with the following measuring apparatus and measurement conditions by the gel permeation chromatography method (GPC) method (polystyrene standard).
Measuring device: “Waters 2695” manufactured by Waters
Detector: “Waters 2414” manufactured by Waters, RI (differential refractometer)
Column: “HSPgel Column, HR MB-L, 3 μm, 6 mm × 150 mm” manufactured by Waters × 2 + “HSPgel Column, HR1, 3 μm, 6 mm × 150 mm” manufactured by Waters × 2
Measurement condition:
Column temperature: 40 ° C
RI detector set temperature: 35 ° C
Developing solvent: Tetrahydrofuran Flow rate: 0.5 ml / min Sample volume: 10 μl
Sample concentration: 0.7 wt%

The polyvinyl acetal resin can be obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like.

Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YL6954, and YL6974 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the polyvinyl acetal resin include the SEREC KS series manufactured by Sekisui Chemical Co., Ltd., and the polyamide resin includes the KS5000 series manufactured by Hitachi Chemical Co., Ltd. and the BP series manufactured by Nippon Kayaku Co., Ltd.

Examples of the polyamideimide resin include KS9000 series manufactured by Hitachi Chemical Co., Ltd.

When a thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and excellent heat resistance, so it maintains a low coefficient of thermal expansion due to a semi-solid or solid epoxy resin and maintains its glass transition point. The resulting cured film has a low thermal expansion coefficient and a high glass transition point in a well-balanced manner. Moreover, since the thermoplastic polyhydroxy polyether resin has a hydroxyl group, it exhibits good adhesion to a semiconductor wafer.

The film property-imparting polymer component may be obtained by block copolymerization of the monomers constituting the above components. The block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain. As the block copolymer, an XYX type or XY-X 'type block copolymer is preferable. Among the XYX type and XYX ′ type block copolymers, the central Y is a soft block and the glass transition temperature (Tg) is low, and X or X ′ on both outer sides is a hard block. Yes What is comprised by the polymer unit whose glass transition temperature (Tg) is higher than a center Y block is preferable. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC). X and X ′ may be different polymer units or the same polymer unit.

Of the XYX type and XYX ′ type block copolymers, X or X ′ is composed of polymer units having a Tg of 50 ° C. or more, and the glass transition temperature (Tg) of Y is More preferred is a block copolymer consisting of polymer units having a Tg of X or X ′ or less. Of the XYX type and XYX ′ type block copolymers, those in which X or X ′ is highly compatible with the curable component described later are preferred, and Y is the curable component. Those having low compatibility are preferred. In this way, a block copolymer in which the blocks at both ends are compatible with the matrix (curable component) and the block at the center is incompatible with the matrix (curable component) is unique in the matrix. It is thought that it becomes easy to show a simple structure.

Among the various polymers described above, phenoxy resin, polyvinyl acetal resin, thermoplastic polyhydroxy polyether resin having a fluorene skeleton, and block copolymer are preferable.

The ratio of the film-forming polymer component occupying all components constituting the semiconductor sealing material is not particularly limited, and is preferably 10 to 50 parts by mass when the total of all components is 100 parts by mass. More preferably, it is 15 to 45 parts by mass.

<Reactive film property-imparting polymer component>
As a component constituting the semiconductor sealing material, a film property-imparting polymer component capable of reacting with a curable component described later may be contained. As such a reactive film imparting polymer, it is preferable to use a carboxyl group-containing resin or a phenol resin. In particular, the use of a carboxyl group-containing resin is preferable because it easily reacts with an epoxy resin when an epoxy resin is included as a curable component, and improves the properties as a semiconductor protective film while imparting film-forming properties.

As the carboxyl group-containing resin, the following resins (1) to (7) can be preferably used.
(1) Dialcohol compounds, polycarbonate-based polyols containing diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid, Carboxyl group-containing urethane resin by polyaddition reaction of diol compounds such as polyether polyols, polyester polyols, polyolefin polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups,
(2) a carboxyl group-containing urethane resin by polyaddition reaction of diisocyanate and a carboxyl group-containing dialcohol compound,
(3) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene,
(4) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional epoxy resin or a bifunctional oxetane resin, and the resulting hydroxyl groups such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing polyester resin to which a dibasic acid anhydride is added,
(5) a carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin and reacting the generated hydroxyl group with a polybasic acid anhydride,
(6) A polybasic acid anhydride is added to a reaction product such as a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound with an alkylene oxide such as ethylene oxide or propylene oxide. And (7) a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide. A carboxyl group-containing resin obtained by reacting a reaction product such as (meth) acrylic acid or the like with an unsaturated group-containing monocarboxylic acid, and further reacting the resulting reaction product with a polybasic acid anhydride,
Etc. can be used suitably. In the present specification, (meth) acrylate means acrylate, methacrylate, and a mixture thereof.

Among the above-described resins, the above (1), (2), (6) and (7) can be used not only as a photosensitive carboxyl group-containing resin but also as a non-photosensitive carboxyl group-containing resin. . Among these, the resins (6) and (7) are preferable because they have a good balance in all properties.

The weight average molecular weight of the reactive film-forming polymer varies depending on the resin skeleton, but is generally preferably in the range of 2 × 10 ³ to 1.5 × 10 ⁵ , more preferably 3 × 10 ³ to 1. The range is × 10 ⁵ , but is not limited to these ranges.

The ratio of the reactive film property-imparting polymer component occupying all the components constituting the semiconductor sealing material is not particularly limited. It is preferable to replace it with a film-imparting polymer.

<Other ingredients>
In addition to the above-described components, various additives may be blended in the semiconductor sealing material according to the present invention as necessary. Examples of various additives include leveling agents, plasticizers, ion scavengers, gettering agents, chain transfer agents, release agents and the like. However, a flame retardant such as antimony trioxide may be blended within a range that does not impair the characteristics, but it is preferable that the flame retardant is not substantially contained from the viewpoint of environmental load.

The thickness of the semiconductor sealing material in the form of a film is not particularly limited as long as it is thicker than the thickness of the semiconductor chip or electronic component to be sealed, but is preferably 3 to 800 μm, more preferably 5 to 700 μm, and particularly preferably. 7 to 600 μm.

The semiconductor sealing material according to the present invention may have a single layer structure or a multilayer structure.

The semiconductor sealing material according to the present invention preferably has a maximum transmittance of 20% or less at a wavelength of 300 to 1200 nm, which is a scale showing at least one of visible light, infrared light and ultraviolet light. More preferably, it is ˜15%, more preferably more than 0% and 10% or less, and particularly preferably 0.001-8%. By setting the maximum transmittance of the semiconductor sealing material at a wavelength of 300 to 1200 nm within the above range, at least one of the visible light wavelength region and the infrared wavelength region is deteriorated in transmittance, and the infrared rays of the semiconductor device are caused. Effects such as prevention of malfunctions and improved visibility of printing. The maximum transmittance of the semiconductor encapsulant at a wavelength of 300 to 1200 nm can be adjusted by the type and content of the colorant component described above. In this specification, the maximum transmittance of the semiconductor encapsulant is 300 of the cured semiconductor encapsulant (thickness 25 μm) using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation). The total light transmittance at ˜1200 nm is measured, and the highest transmittance value (maximum transmittance) is assumed.

The form of the semiconductor sealing material according to the present invention may be liquid, granule, tablet, or sheet, but preferably has a sheet form because it can be easily handled.

<Manufacturing method of sealing material for semiconductor>
The semiconductor sealing material according to the present invention is obtained by using a composition (mixture) obtained by mixing the above-described components at a predetermined ratio. The composition may be previously diluted with a solvent, or may be added to the solvent during mixing. Moreover, when producing the sealing material for semiconductors using a composition, you may dilute a composition with a solvent. Examples of the solvent include ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, cyclohexane, toluene, heptane and the like. By this method, a liquid semiconductor sealing material can be obtained.

The composition (mixture) prepared as described above is coated on a support and formed into a film, whereby a sheet-like semiconductor sealing material can be obtained. As a film forming method, a conventionally known method can be applied, and a composition (mixture) is coated on a support by a known means such as a flat plate press method, a roll knife coater, a gravure coater, a die coater, or a reverse coater. By processing and drying, a semiconductor sealing material can be obtained. Moreover, the semiconductor sealing material having the above-described thickness can be obtained by adjusting the coating amount of the composition (mixture).

As the support, conventionally known materials such as a separate paper, a separate film, a separate paper, a release film and a release paper can be suitably used. Also, release on one or both sides of a release paper substrate made of a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as stretched polypropylene film (OPP), or a plastic film such as polyimide film. You may use what formed the layer. The release layer is not particularly limited as long as it has a release property, and examples thereof include silicone resins, organic resin-modified silicone resins, and fluororesins.

The semiconductor sealing material of the present invention can also be used as a sealing material for printed wiring boards, a sealing material for solar cell materials, and an adhesive between an electric wire / cable sealing material substrate and a semiconductor chip. In particular, the semiconductor encapsulant of the present invention includes a semiconductor chip, a semiconductor encapsulant that embeds the semiconductor chip so that the circuit formation surface of the semiconductor chip is exposed on the surface, and the circuit formation surface side of the semiconductor chip. The rewiring layer can be suitably used for a fan-out type wafer level package provided in a semiconductor sealing material region other than the semiconductor chip region.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” means parts by mass.

<Synthesis of Reactive Film Property-Providing Polymer (Carboxyl Group-Containing Resin) 1>
Into an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, a bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120) 0 g, 1.20 g of potassium hydroxide and 120.0 g of toluene were charged, the inside of the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours.

Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of bisphenol A-formaldehyde type phenol resin was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring.

12.6 g of water produced by the reaction was distilled as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of propylene glycol monomethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.

Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to give a solid film with an acid value of 88 mg KOH / g and a non-volatile content of 71%. Containing resin) 1 was obtained. This is designated as resin solution A. The weight average molecular weight of one component of the reactive film-imparting polymer (carboxyl group-containing resin) contained in the resin solution A was 4 × 10 ³ .

The value of the weight average molecular weight (Mw) was measured by the gel permeation chromatography method (GPC) method (polystyrene standard) under the following measuring apparatus and measurement conditions.
Measuring device: “Waters 2695” manufactured by Waters
Detector: “Waters 2414” manufactured by Waters, RI (differential refractometer)
Column: “HSPgel Column, HR MB-L, 3 μm, 6 mm × 150 mm” by Waters × 2 + “HSPgel Column, HR 1, 3 μm, 6 mm × 150 mm” by Waters × 2
Measurement condition:
Column temperature: 40 ° C
RI detector set temperature: 35 ° C
Developing solvent: Tetrahydrofuran Flow rate: 0.5 ml / min Sample volume: 10 μl
Sample concentration: 0.7 wt%

<Preparation of semiconductor sealing material 1>
The following components were dissolved and dispersed in methyl ethyl ketone to prepare a composition solution 1 for a sealing material having a solid content mass concentration of 20%.
・ 2 parts of anthraquinone ・ 50 parts of phenoxy resin (FX293 made by Tohto Kasei Co., Ltd.) ・ 70.4 parts of resin solution A ・ 30 parts of naphthalene type epoxy resin (NC-7000 made by Nippon Kayaku Co., Ltd.) ・ Bixylenol type epoxy resin (Mitsubishi Chemical) YX-4000) 10 parts, phenol novolac type epoxy resin 10 parts (DEN-431, manufactured by The Dow Chemical Company)
・ Carbon black (Carbon MA-100 manufactured by Mitsubishi Chemical Corporation) 10 parts ・ Spherical silica (Admafine SO-E2 manufactured by Admatechs) 200 parts ・ Aluminum hydroxide (Showa Denko Hydylite 42M) 150 parts ・ Silane Coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 2 parts 2-phenylimidazole (2PZ, Shikoku Kasei Kogyo Co., Ltd.) 2 parts

The composition solution 1 for sealing material was applied to a polyethylene terephthalate film (PET film) whose surface was subjected to a release treatment, and dried at 100 ° C. for 10 minutes to prepare a sealing material 1 for semiconductor having a thickness of 50 μm. Six films were laminated to produce a semiconductor sealing material 1 having a thickness of 300 μm.

<Preparation of semiconductor sealing material 2>
The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 120 ° C. for 6 minutes, and melt-kneaded while reducing pressure (0.01 kg / cm ² ) for a total of 10 minutes to prepare kneaded product 2 .
・ Anthraquinone 2 parts ・ Naphthalene type epoxy resin (Nippon Kayaku NC-7000) 30 parts ・ Bixylenol type epoxy resin (Mitsubishi Chemical YX-4000) 10 parts ・ Phenol novolac type epoxy resin 10 parts (The Dow)・ DEN-431 manufactured by Chemical Company
・ Carbon black (Carbon MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) 10 parts ・ Spherical silica (Admafine SO-E2 manufactured by Admatechs) 500 parts ・ Silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts ・ 2- 2 parts of phenylimidazole (2PZ manufactured by Shikoku Chemicals Co., Ltd.)

The obtained kneaded material 2 is arranged so as to be sandwiched between two 50 μm cover films (Teijin Purex film), and the kneaded material is formed into a sheet by a flat plate pressing method. A stop material 2 was obtained.

<Preparation of semiconductor sealing material 3>
The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 120 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total while reducing the pressure (0.01 kg / cm ² ) to prepare a kneaded product 3 .
・ Manganese dioxide 5 parts ・ Epoxy resin (trade name Epicoat 1001; manufactured by JER) 30 parts ・ Phenol novolac type epoxy resin 10 parts (DEN-431 manufactured by The Dow Chemical Company)
・ C. I. Pigment Blue 15: 3 0.8 part C.I. I. Pigment Yellow 147 0.55 part, Paliogen Red K3580 1.5 parts, spherical silica (Admafine SO-E2 manufactured by Admatechs) 400 parts, silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 2 parts 2- 2 parts of phenylimidazole (2PZ manufactured by Shikoku Chemicals Co., Ltd.)

The obtained kneaded material 3 is arranged so as to be sandwiched between two 50 μm PET films (Teijin Purex film), and the kneaded material is formed into a sheet shape by a flat plate pressing method. A stop material 3 was obtained.

<Preparation of Semiconductor Sealant 4>
The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 120 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total while reducing pressure (0.01 kg / cm ² ) to prepare kneaded product 4 .
・ Benzoyl peroxide 3 parts ・ Naphthalene type epoxy resin (Nippon Kayaku NC-7000) 30 parts ・ Bixylenol type epoxy resin (Mitsubishi Chemical YX-4000) 10 parts ・ Phenol novolac type epoxy resin 10 parts (The・ DEN-431 manufactured by Dow Chemical Company
・ Carbon black (Carbon MA-100 made by Mitsubishi Chemical Corporation) 10 parts ・ Spherical silica (Admafine SO-E2 made by Admatechs) 600 parts ・ Titanium oxide (CR-90 made by Ishihara Sangyo Co., Ltd.) 15 parts ・ Silane cup Ring agent (KBE-403, Shin-Etsu Chemical Co., Ltd.) 2 parts 2-phenylimidazole (2PZ, Shikoku Chemicals Co., Ltd.) 2 parts

The obtained kneaded product 4 is arranged so as to be sandwiched between two 50 μm cover films (Teijin Purex film), and the kneaded product is formed into a sheet by a flat plate pressing method. A stop material 4 was obtained.

<Preparation of semiconductor sealing material 5>
The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 120 ° C. for 6 minutes, and melt-kneaded while reducing pressure (0.01 kg / cm ² ) for a total of 10 minutes to prepare kneaded product 5 .
・ Anthraquinone (molecular weight 208) 3 parts ・ Antioxidant (Adekastab AO-60) 1 part ・ Naphthalene type epoxy resin (NC-7000, Nippon Kayaku Co., Ltd.) 30 parts ・ Bixylenol type epoxy resin (YX-, manufactured by Mitsubishi Chemical Corporation) 4000) 10 parts ・ Phenol novolac type epoxy resin 10 parts (DEN-431 manufactured by The Dow Chemical Company)
・ Carbon black (Carbon MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) 10 parts ・ Spherical silica (Admafine SO-E2 manufactured by Admatechs) 500 parts ・ Silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts ・ 2- Phenylimidazole (2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) 2 parts In the semiconductor sealing material 5, the number of moles of the functional group of the antioxidant is 100% Then, it becomes about 12%.

The obtained kneaded product 5 is placed so as to be sandwiched between two 50 μm cover films (Teijin Purex film), and the kneaded product is formed into a sheet by a flat plate pressing method. A stop material 5 was obtained.

<Preparation of semiconductor sealing material 6>
A semiconductor encapsulant 6 having a thickness of 300 μm was produced in the same manner as in the semiconductor encapsulant 1 except that no anthraquinone was used.

<Preparation of semiconductor sealing material 7>
A semiconductor encapsulant 7 having a thickness of 300 μm was produced in the same manner as in the semiconductor encapsulant 2 except that no anthraquinone was used.

<Preparation of semiconductor sealing material 8>
A semiconductor encapsulant 8 having a thickness of 300 μm was produced in the same manner as in the semiconductor encapsulant 3 except that manganese dioxide was not used.

<Preparation of semiconductor sealing material 9>
A semiconductor encapsulant 9 having a thickness of 300 μm was produced in the same manner as in the semiconductor encapsulant 4 except that benzoyl peroxide was not used.

<Preparation of semiconductor sealing material 10>
A semiconductor encapsulant 10 having a thickness of 300 μm was produced in the same manner as in the semiconductor encapsulant 5 except that anthraquinone and Adeka Stab AO-60 were not used.

<Preparation of semiconductor wafer>
As a semiconductor wafer, a P-type silicon wafer polished to a 4-inch thickness of 200 μm in which a 100 nm SiO ₂ film was formed on one side made by Canosis Co., Ltd. was prepared.

<Fabrication of semiconductor packages>
The above semiconductor wafer was diced using a dicing apparatus to obtain a 10 mm × 10 mm square semiconductor chip. A temporarily fixed film was disposed on a SUS flat substrate, and the semiconductor chip was further disposed such that the SiO ₂ surface was in contact with the temporarily fixed film. A 20 mm × 20 mm square sheet-shaped semiconductor encapsulant was laminated thereon so that the center positions were approximately the same, and compression-molded at 150 ° C. for 1 hour using a heating type press crimping machine. The temporarily fixed film was peeled off from the obtained laminate to obtain a semiconductor package.

Adhesion was evaluated as a method for confirming suppression of gap formation between a semiconductor chip and a semiconductor sealing material. Evaluation was performed as follows.
<Evaluation>
Prepare a 2.38% TMAH 2.38% aqueous solution (trade name AD-10, manufactured by Tama Chemical Industry Co., Ltd.) at 25 ° C., and immerse the semiconductor package produced here with the SiO ₂ surface of the semiconductor chip facing up for 5 minutes. Processed. Thereafter, the semiconductor package was taken out and rinsed twice with pure water. Thereafter, moisture was blown off by air blow, and the mixture was collected on a hot plate set at 100 ° C. for 5 minutes. As for the obtained semiconductor package after processing, the boundary part between the semiconductor chip and the sealing material is observed with an optical microscope and an electron microscope from the semiconductor chip side. The thing was determined as x. The evaluation results were as shown in Table 1 below.

As is clear from the evaluation results shown in Table 1, in Examples 1 to 5 using the semiconductor encapsulant containing an oxidant, the boundary between the semiconductor chip and the encapsulant was adhered even after the alkali treatment. It was good. On the other hand, in Comparative Examples 1 to 5 using the semiconductor encapsulant containing no oxidizer, a gap was generated at the boundary between the semiconductor chip and the encapsulant due to the alkali treatment. As estimated, in the semiconductor wafers of Examples 1 to 5, the surface of Si, which is a semiconductor chip, is oxidized by the oxidant contained in the semiconductor sealing material, and a thin film made of SiO ₂ is formed. It is considered that the etching of the side surface of the semiconductor chip due to the alkali treatment was suppressed.

Claims

A semiconductor encapsulant comprising an oxidant capable of oxidizing a semiconductor.
The semiconductor sealing material according to claim 1, comprising a curable component, a curing agent component, a curing accelerator component, and an inorganic filler.
The sealing material for semiconductor according to claim 1, which has a sheet-like shape.
2. The semiconductor sealing material according to claim 1, which is used for a fan-out type wafer level package.