CN108369928B - Sealing material for semiconductor - Google Patents
Sealing material for semiconductor Download PDFInfo
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- CN108369928B CN108369928B CN201680073780.XA CN201680073780A CN108369928B CN 108369928 B CN108369928 B CN 108369928B CN 201680073780 A CN201680073780 A CN 201680073780A CN 108369928 B CN108369928 B CN 108369928B
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- semiconductor
- sealing material
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- semiconductor chip
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Abstract
Provided is a semiconductor sealing material which can prevent a gap from being formed between a semiconductor chip and the semiconductor sealing material. The sealing material for a semiconductor of the present invention is characterized by containing an oxidizing agent capable of oxidizing a semiconductor.
Description
Technical Field
The present invention relates to a sealing material for a semiconductor for protecting a semiconductor chip, and more particularly, to a sealing material for a semiconductor used in a Fan-out wafer level package in which an arrangement region of an external connection electrode is larger than a planar size of the semiconductor.
Background
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 this demand, semiconductor circuits are sometimes mounted in packages close to the Chip Size (Chip Size packages). As one of means for realizing a chip size Package, a packaging method called a Wafer Level Package (hereinafter, may be abbreviated as WLP) has been proposed in which a Wafer is bonded and fragmented at a Wafer Level. WLP is attracting attention because it can contribute to cost reduction and miniaturization. The WLP is flip-chip mounted on the circuit substrate on which the electrodes are formed.
In addition, with the miniaturization and high integration of semiconductor chips, the number of electrodes (terminals and bumps) for external connection of the semiconductor chips tends to increase, and thus the pitch of the electrodes for external connection of the semiconductor chips tends to decrease. However, it is not always easy to directly mount a semiconductor chip having bumps formed at a fine pitch on a circuit board.
To solve the above problems, the following proposals are made: a region of the semiconductor sealing material is formed on the outer periphery of the semiconductor chip, and a rewiring layer connected to the electrode is provided in the region of the semiconductor sealing material, thereby increasing the pitch of the bumps. Such a WLP is called a fan-out wafer level package (hereinafter, abbreviated as FO-WLP) because the size of the arrangement region of the bump is increased relative to the size of the semiconductor chip.
In FO-WLP, a semiconductor chip is embedded in 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 an electrode of the semiconductor chip is also provided in a region of the semiconductor sealing material in which the semiconductor chip is embedded, and the bump is electrically connected to the electrode of the semiconductor chip via the rewiring layer. The pitch of the bumps may be set to be larger than the pitch of the electrodes of the semiconductor chip.
In addition, it is also conceivable to store a plurality of electronic components in one package in addition to the semiconductor chip, or to form one semiconductor component by embedding a plurality of semiconductor chips in a sealing material for a semiconductor. In such a package, a plurality of electronic components are embedded in a semiconductor sealing material. A redistribution layer connected to an electrode of an electronic component is provided in a semiconductor sealing material in which a plurality of electronic components are embedded, and a bump is electrically connected to the electrode of the electronic component via the redistribution layer. In this case, the size of the bump arrangement region is also increased relative to the size of the semiconductor chip, and therefore, can be referred to as FO-WLP.
In such a package, a semiconductor chip or an electronic component is usually arranged on a support at a predetermined interval, and the semiconductor chip or the electronic component is embedded in a sealing material for a semiconductor, and after the sealing material is cured by heating, the semiconductor chip or the electronic component is peeled off from the support to produce a pseudo wafer. Next, a rewiring layer is formed from the semiconductor chip circuit surface of the dummy wafer to the expanded region of the semiconductor sealing material. 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, a positive type photosensitive resin is generally applied to a semiconductor chip circuit surface of a dummy wafer and prebaked, and an area to be opened is irradiated with active light such as UV light through a photomask or the like, and then developed with a developing solution such as TMAH (tetramethylammonium hydroxide), and heat curing, oxygen plasma treatment, or the like are performed to perform sputtering of a metal electrode, and further a photoresist layer is formed and the wiring pattern is formed to form the rewiring layer (for example, patent document 1 or the like).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-38270
Disclosure of Invention
Problems to be solved by the invention
However, when FO-WLP is produced through the above-described steps, a gap is generated at the boundary between the semiconductor chip and the semiconductor sealing material, and there is a problem that the reliability of the rewiring layer formed later is lowered. In addition, there is a problem that the product reliability of the completed FO-WLP is lowered due to the gap.
Accordingly, an object of the present invention is to provide a sealing material for a semiconductor, particularly a sealing material for FO-WLP, which can suppress formation of a gap between a semiconductor chip and the sealing material for a semiconductor.
Means for solving the problems
The present inventors have made detailed studies on the phenomenon in which a boundary between a semiconductor chip and a sealing material for a semiconductor is generated, and as a result, have found that the gap is generated in a developing step used when forming a rewiring layer. As a result of further studies, it has been found that, in the developing step, the developing solution also penetrates into the boundary between the side surface of the semiconductor chip embedded in the semiconductor sealing material and, in some cases, penetrates into the semiconductor sealing material, and the penetrating or penetrated developing solution etches the side surface of the semiconductor chip, thereby forming a gap between the side surface of the semiconductor chip and the boundary between the semiconductor sealing material and the side surface of the semiconductor chip.
Further, the present inventors have conducted extensive studies based on the above findings and as a result, have found that, by adding a component which does not etch the semiconductor wafer with a developer to the semiconductor sealing material in advance, formation of a gap at the boundary between the semiconductor chip side surface and the semiconductor sealing material can be suppressed even when a developer is used in formation of a rewiring layer, as a result, formation of the rewiring layer is facilitated, and the reliability of the completed FO-WLP can be improved.
The sealing material for a semiconductor of the present invention is characterized by containing an oxidizing agent capable of oxidizing a semiconductor.
In the embodiment of the present invention, the sealing material for a semiconductor may contain a curable component, a curing agent component, a curing accelerator component, and an inorganic filler.
In the embodiment of the present invention, the sealing material for a semiconductor may have a sheet shape.
The present invention can be used for a fan-out type wafer level package.
ADVANTAGEOUS EFFECTS OF INVENTION
The sealing material for a semiconductor of the present invention can suppress formation of a gap between a semiconductor chip and the sealing material for a semiconductor, particularly for FO-WLP. As a result, the formation of the rewiring layer during the fabrication of the FO-WLP can be facilitated, and the reliability of the completed FO-WLP can be improved.
Detailed Description
The semiconductor sealing material protects a semiconductor element (for example, a semiconductor chip) formed by processing a semiconductor wafer from heat and dust, and is sealed and insulated so as to cover the entire semiconductor element. The sealing material for a semiconductor includes the components described below as a sealing material, and the sealing material for a semiconductor of the present invention is characterized by including an oxidizing agent capable of oxidizing a semiconductor. As described above, for example, in the production of FO-WLP, a rewiring layer is formed on the semiconductor chip circuit surface of a dummy wafer in which semiconductor chips and the like are embedded with a semiconductor sealing material, and a developing solution such as TMAH is used in the formation of the rewiring layer by patterning. During the development treatment, the developer enters into 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 TMAH developer, and a gap is formed between the semiconductor wafer and the semiconductor sealing material that are embedded. In the present invention, the sealing material for a semiconductor comprisesAn oxidizing agent capable of oxidizing the semiconductor wafer, and therefore, when the semiconductor chip is sealed with the sealing material for a semiconductor, the surface of the semiconductor chip is oxidized. For example, in the case of a silicon (Si) semiconductor chip, SiO is formed on the surface of the semiconductor chip2The film is extremely thin. Therefore, it is considered that even if the developing solution is immersed in the interface between the semiconductor chip and the sealing material for semiconductor in the subsequent development treatment, the oxide film (SiO) can be used2) The etching of the silicon semiconductor by the developing solution is suppressed. This is merely a presumption of the inventors and the invention is not limited to this logic.
Examples of the semiconductor chip sealed with the sealing material for a semiconductor 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, and may be any of an organic oxidizing agent and an inorganic oxidizing agent, and preferably an organic oxidizing agent is used in view of compatibility with other components constituting the sealing material for a semiconductor, which will be described later.
As the organic oxidizing agent, an organic oxidizing agent or an organic peroxide can be preferably used. Examples of the organic oxidizing agent include hydrogen peroxides, 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, diacetyl peroxide, and the like.
Examples of the hydrogen peroxide include t-butyl hydroxide, cumene hydroxide, bis (trimethylsilyl) peroxide, ethyl hydroperoxide, t-butyl hydroperoxide, succinic acid peroxide, and 1,1,3, 3-tetramethylbutyl hydroperoxide.
Examples of quinones include p-chloranil (tetrachloro-p-benzoquinone), o-chloranil, tetrabromo-1, 4-benzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, chloranil, dichlorobenzoquinone, benzoquinone, naphthoquinone, anthraquinone, substituted anthraquinones, and 2,3,5, 6-tetrachloro-p-benzoquinone.
Examples of the pyridine include pyridine oxide, pyridine N-oxide, dimethylaminopyridine oxide, 2,6, 6-tetramethyl-1-piperidyl oxide and trimethylamine N-oxide.
Examples of the organic nitro compound include m-nitrobenzenesulfonate, p-nitrobenzoate, nitroguanidine (ニトロガニジン), and aromatic nitrosulfonate.
Further, commercially available peroxides may be used, and for example, peroxyketals sold under the trade names Pertetra A, Perhexa HC, Perhexa C, Perhexa V, and Perhexa 22 by Nippon oil and fat Co; hydrogen peroxides sold under the trade names Perbutyl H, Percumyl P, Permenta H, Perocta H; dialkyl peroxides sold under the tradenames Perbutyl C, Perbutyl D, Perhexyl D; diacyl peroxides sold under the trade names PEROYL IB, PEROYL 355, PEROYL L SA, NYPER BW, NYPER BMT-K40, NYPER BMT-M; peroxydicarbonates sold under the tradenames PEROYL IPP, PEROYL NPP, PEROYL TCP, PEROYL OPP, PEROYL SBP; peroxyesters sold under the tradenames Percumyl ND, Perocta ND, Perhexa ND, Perbutyl ND, Perhexa PV, Perbutyl PV, Perhexa 25O, Perocta O, Perhexa O, Perbutyl L, Perbutyl 355, Perhexa I, Perbutyl E, Perhexa 25Z, Perbutyl A, Perhexa Z, Perbutyl ZT, Perbutyl Z, and ペロマー AC, BTTB-25.
The oxidizing agent may be used alone or in combination of two or more.
In the present invention, among the above-mentioned oxidizing agents, organic peroxides and quinones are preferably used in view of compatibility between reactivity (oxidizing property) with a semiconductor in which an oxide layer is formed on the surface of a semiconductor chip and stability as a sealing material for a semiconductor.
Examples of the inorganic oxidizing agent 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 in terms of the balance between reactivity as an oxidizing agent and stability as a sealing material. Among the above-mentioned oxidizing agents, organic oxidizing agents are preferred because they can be homogeneously mixed with the resin component of the semiconductor sealing material as compared with inorganic oxidizing agents, and as a result, they act more homogeneously with the resin component adhering to the surface of the semiconductor chip, and thus they are excellent in moisture resistance, and as a result, they further improve the reliability of suppressing the formation of gaps.
The content of the oxidizing agent is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.05 to 8 parts by mass, and particularly preferably in the range of 0.1 to 5 parts by mass, when the total mass of the components other than the oxidizing agent in terms of solid content is taken as 100 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 oxidatively decomposing the sealing material for a semiconductor.
As described above, depending on the type of the oxidizing agent, the resin component constituting the sealing material for a semiconductor may be oxidized. Therefore, in the present invention, an antioxidant may be contained in the semiconductor sealing material. Examples of the antioxidant include a phenol-based antioxidant or an amine-based antioxidant which functions as a radical chain inhibitor, a phosphorus-based antioxidant which functions as a peroxide decomposer, a sulfur-based antioxidant, a hydrazine-based antioxidant which functions as a metal deactivator, and an amide-based antioxidant. Among these, phenol-based antioxidants or amine-based antioxidants can be preferably used. Commercially available antioxidants may also be used, for example, ADKSTAB AO-20, AO-30, AO-40, AO-50F, AO-60, AO-60G, AO-80, AO-330, ADKSTAB PEP-36/36A, HP-10, 2112RG, PEP-8W, 1178, 1500, C, 135A, 3010, TPPADEKASTAB AO-412S, AO-503, and the like.
When the semiconductor sealing material of the present invention contains an antioxidant, the content thereof is preferably in the range of 5 to 99% by mole, more preferably in the range of 8 to 90% by mole, and particularly preferably in the range of 10 to 80% by mole, based on 100% by mole of the functional group of the oxidant. By setting the content of the antioxidant within the above range, the reactivity of the oxidant can be adjusted while maintaining the reactivity (oxidizing property) of the oxidant with the semiconductor, and oxidative decomposition of the resin component can be suppressed.
The semiconductor sealing material of the present invention may contain a curable component, a curing agent component, a curing accelerator component, an inorganic filler, and the like, which will be described later. The following describes components other than the oxidizing agent and the antioxidant constituting the sealing material for a semiconductor.
< curable Components >
The curable component of the sealing material for a semiconductor is not particularly limited, and conventionally known resins, preferably epoxy resins, can be used. The epoxy resin has a solid, semi-solid, or liquid state in a shape before reaction. These may be used alone or in combination of two or more. When the epoxy resin containing halogen is used, the epoxy resin is preferably halogen-free since the action of reducing the reactivity of the added oxidizing agent, that is, the inhibition of the formation of the gap may be affected by the redox reaction between the halide ion generated by hydrolysis and the oxidizing agent, and particularly preferably the halogen is substantially free of chlorine, bromine, or iodine.
Specifically, it is preferable that the epoxy resin has a chlorine content of 2500ppm or less, a bromine content of 1000ppm or less, and a total content of chlorine and bromine of 3000ppm or less. The chlorine content is more preferably 2000ppm or less, still more preferably 1500ppm or less, and particularly preferably 1000ppm or less. The sealing material is also preferably halogen-free, and more specifically, it is preferably 900ppm or less in chlorine content, 900ppm or less in bromine content, and 1500ppm or less in the total content of chlorine and bromine. The halogen content can be measured by a flask combustion treatment ion chromatography method based on the JPCA standard.
Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (4-functional naphthalene type epoxy resin) manufactured by DIC, and NC-7000 (polyfunctional solid epoxy resin having a naphthalene skeleton) manufactured by Nippon Chemicals; an epoxide (triphenol epoxy resin) of a condensate of a phenol such as EPPN-502H (triphenol epoxy resin) manufactured by japan chemical company and an aromatic aldehyde having a phenolic hydroxyl group; dicyclopentadiene aralkyl type epoxy resins such as EPICLON HP-7200H (a multifunctional solid epoxy resin having a dicyclopentadiene skeleton) manufactured by DIC; biphenyl aralkyl type epoxy resins such as NC-3000H (multifunctional solid epoxy resin having a biphenyl skeleton) manufactured by japan chemical company; biphenyl/phenol novolac type epoxy resins such as NC-3000L manufactured by japan chemical company; novolac type epoxy resins such as EPICLON 660 and EPICLON 690 manufactured by DIC, and EOCN-104S manufactured by Nippon Kagaku; biphenyl type epoxy resins such as YX-4000 manufactured by Mitsubishi chemical corporation; phosphorus-containing epoxy resins such as TX0712 manufactured by new-day iron-on-gold chemical company; tris (2, 3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan chemical industries, Ltd.
Examples of the semi-solid epoxy resin include bisphenol A type epoxy resins such as EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822, EPICLON YD-134 manufactured by Tokyo Chemicals, jER834 and jER872 manufactured by Mitsubishi chemical industries, and ELA-134 manufactured by Sumitomo chemical industries; naphthalene type epoxy resins such as EPICLON HP-4032 manufactured by DIC corporation; and phenol novolac epoxy resins such as EPICLON-740 manufactured by DIC.
Examples of the liquid epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, glycidyl amine type epoxy resin, aminophenol type epoxy resin, and alicyclic epoxy resin.
The curable components may be used singly or in combination of two or more. The compounding amount of the curable component is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total solid components constituting the sealing material for a semiconductor. The amount of the liquid epoxy resin blended is preferably 0 to 45 parts by mass, more preferably 0 to 30 parts by mass, and particularly preferably 0 to 5 parts by mass, based on 100 parts by mass of the curable component. When the 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 the crack resistance may be improved.
< curing agent component >
The semiconductor sealing material of the present invention may contain a curing agent component. The curing agent component has a functional group that reacts with the curable component. Examples of such a curing agent component include phenol resins, polycarboxylic acids and anhydrides thereof, cyanate resins, and active ester resins, and phenol resins are preferred. These may be used alone or in combination of two or more.
As the phenol resin, conventionally known phenol resins such as phenol novolac resin, alkylphenol novolac resin, bisphenol a novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, cresol/naphthol resin, polyvinyl phenol, phenol/naphthol resin, phenol resin containing an α -naphthol skeleton, triazine-containing cresol phenol novolac resin and the like can be used singly or in combination of two or more.
The polycarboxylic acid and its anhydride are compounds having two or more carboxyl groups in one molecule and their anhydrides, and examples thereof include copolymers of (meth) acrylic acid, copolymers of maleic anhydride, condensates of dibasic acid, and resins having a carboxylic acid terminal such as carboxylic acid terminal imide resins.
The cyanate ester resin is a compound having two or more cyanate groups (-OCN) in one molecule. Any cyanate resin known in the art can be used as the cyanate resin. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolac 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. In addition, a prepolymer in which partial triazination is performed may be used.
The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can be generally obtained by a condensation reaction of a carboxylic acid compound and a hydroxyl compound. Among them, as the hydroxyl compound, an active ester compound obtained by using a phenol compound or a naphthol compound is preferably used. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenol novolak, and the like.
As the curing agent component, alicyclic olefin polymers other than the above may be used. Examples of alicyclic olefin polymers that can be preferably used include: (1) an alicyclic olefin having at least either a carboxyl group or a carboxylic anhydride group (hereinafter referred to as "carboxyl group or the like") is polymerized together with other monomers as required; (2) a (co) polymer obtained by polymerizing an aromatic olefin having a carboxyl group or the like with another monomer as required, the aromatic ring portion of which is hydrogenated; (3) a copolymer obtained by copolymerizing an alicyclic olefin having no carboxyl group or the like with a monomer having a carboxyl group or the like; (4) a copolymer obtained by copolymerizing an aromatic olefin having no carboxyl group or the like with a monomer having a carboxyl group or the like, the aromatic ring portion of which is hydrogenated; (5) a substance obtained by introducing a compound having a carboxyl group or the like into an alicyclic olefin polymer having no carboxyl group or the like by a modification reaction; or (6) a substance obtained by converting the carboxylic acid ester group of the alicyclic olefin polymer having a carboxylic acid ester group obtained in the above (1) to (5) into a carboxyl group by, for example, hydrolysis; and so on.
Among the above curing agent components, phenol resins, cyanate resins, active ester resins, and alicyclic olefin polymers are preferable. In particular, a phenol resin is more preferably used because it has high polarity and is easy to suppress the relative dielectric constant.
The curing agent component is preferably contained in such a ratio that the ratio of functional groups (functional groups capable of undergoing a curing reaction) such as epoxy groups of the curable component to the functional groups of the curing agent component capable of reacting with the functional groups (ratio of the number of functional groups of the curing agent component to the number of functional groups of the curable component: equivalent) is 0.2 to 5. By setting the equivalent ratio within the above range, a semiconductor sealing material having more excellent protective properties can be obtained.
< curing Accelerator component >
The semiconductor sealing material of the present invention may contain a curing accelerator component. The curing accelerator component is a substance that accelerates the curing reaction of the curable component, and can further improve the adhesion and heat resistance of the sealing material to the semiconductor wafer. Examples of the curing accelerator component include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea derivatives, melamine, and polyhydrazide; at least any one of organic acid salts and epoxy adducts thereof; an amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-s-triazine, 2, 4-diamino-s-triazine, and 2, 4-diamino-6-xylyl-s-triazine; amines such as trimethylamine, triethanolamine, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4, 6-tris (dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2, 5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4, 6-triphenylthiopyranium hexafluorophosphate and the like; styrene-maleic anhydride resin; an equimolar reaction product of phenyl isocyanate and dimethylamine, an equimolar reaction product of organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate and dimethylamine, a conventionally known curing accelerator such as a metal catalyst, and these may be used singly or in combination of two or more.
The curing accelerator component is not essential, and when it is particularly desired to accelerate the curing reaction, it is preferably used in a range of 0.01 to 20 parts by mass per 100 parts by mass of the curable component. When a metal catalyst is used as the curing accelerator component, the content thereof is preferably 10ppm to 550ppm, preferably 25ppm to 200ppm in terms of metal, relative to 100 parts by mass of the curable component.
< inorganic Filler component >
The sealing material for a semiconductor of the present invention may contain an inorganic filler component. By containing the inorganic filler component, the reliability of the sealing material for a semiconductor is improved. In addition, when the back surface of the semiconductor sealing material or the like is laser-marked, the inorganic filler component is exposed at the portion cut off by the laser light, and the reflected light is diffused, thereby showing a color close to white. Thus, when the semiconductor sealing material contains a colorant component described later, the laser marking portion and the other portions have a poor contrast, and the marking (printing) becomes clear.
As the inorganic filler component, conventionally known inorganic filler components can be used without limitation, and examples thereof include powders of silica, alumina, talc, aluminum hydroxide, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, and the like, beads obtained by spheroidizing these powders, single crystal fibers, glass fibers, and the like, and one kind or two or more kinds of them can be used singly or in combination. Among these, silica, alumina and titania are preferable.
The inorganic filler component preferably has an average particle diameter of 0.01 to 15 μm, more preferably 0.02 to 12 μm, and particularly preferably 0.03 to 10 μm. In the present specification, the average particle diameter is determined by measuring the major axis diameter of 20 inorganic filler components selected at random by an electron microscope, and the number average particle diameter calculated as the arithmetic average thereof is the average particle diameter.
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, based on 100 parts by mass of the total solid components constituting the sealing material for a semiconductor.
< colorant component >
The semiconductor sealing material of the present invention may contain a colorant component. By containing the colorant component, it is possible to prevent an operation error of the semiconductor device due to infrared rays generated from peripheral devices or the like when the semiconductor chip provided with the protective film is incorporated into the device. In addition, when the protective film is marked with a mark by means of laser marking or the like, the mark such as a character or a symbol is easily recognized. That is, in a semiconductor chip having a protective film formed thereon, a part number or the like is usually printed on the surface of the protective film by a laser marking method (a method of cutting the surface of the protective film by laser and printing the same), and by including a colorant in the protective film, a difference in contrast between a portion of the protective film cut by laser and a portion other than the portion can be sufficiently obtained, and visibility is improved.
As the colorant component, one or a combination of two or more of organic or inorganic pigments and dyes may be used, and among these, a black pigment is preferable from the viewpoint of electromagnetic wave or infrared ray shielding properties. As the black pigment, carbon black, perylene black, iron oxide, aniline black, activated carbon, and the like are used, but not limited thereto. Carbon black is particularly preferable in terms of preventing operational failure of the semiconductor device. Instead of carbon black, pigments such as red, blue, green, and yellow may be mixed to form black or a black color close to black.
The colorant component is contained in a proportion of preferably 0.1 to 35 parts by mass, more preferably 0.5 to 25 parts by mass, and particularly preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total solid content constituting the sealing material for a semiconductor.
< coupling agent component >
In order to improve at least one of the adhesiveness to an adherend (semiconductor wafer), the adhesion, and the cohesiveness of the protective film of the sealing material for a semiconductor, a coupling agent component having a functional group reactive with an inorganic substance and a functional group reactive with an organic functional group may be contained. In addition, by including the coupling agent component, the heat resistance of the protective film obtained by curing the sealing material for a semiconductor is not impaired, and the water resistance thereof can be improved. Examples of such a coupling agent include titanate-based coupling agents, aluminate-based coupling agents, and silane coupling agents. Among these, silane coupling agents are preferable.
Examples of the organic group contained in the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group, and an isocyanate group. As the silane coupling agent, commercially available ones can be used, and examples thereof include 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-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, and KBE-9007 (trade names; manufactured by Shin-Etsu Silicone Co., Ltd.). These may be used alone or in combination of two or more.
< component of Polymer for imparting film Property >
The semiconductor sealing material of the present invention may be in the form of liquid, pellets, sheets, or the like. In the case of forming a sheet-like sealing material for a semiconductor, a polymer component (film-forming polymer) imparting film-forming properties may be added. In the present specification, the film-forming property imparting polymer component refers to a polymer component having no reactive functional group, for the purpose of distinguishing from a film-forming property imparting polymer component having a reactive property described later. Examples of such a film-forming property-imparting polymer component include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various 2-functional phenolic compounds, a phenoxy resin in which the hydroxyl group of a hydroxyether moiety present in the skeleton thereof is esterified with various acid anhydrides or acid chlorides, a polyvinyl acetal resin, a polyamide resin, a polyamideimide resin, a block copolymer, and the like. These polymers may be used singly 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 2X 104Above, preferably 2 × 104～3×106。
In the present specification, the value of the weight average molecular weight (Mw) can be measured by a Gel Permeation Chromatography (GPC) method (polystyrene standard) using the following measurement apparatus and measurement conditions.
A measuring device: waters manufactures "Waters 2695"
A detector: waters manufactures "Waters 2414", RI (differential refractometer)
Column: "HSP gel column, HR MB-L,3 μm,6 mm. times.150 mm". times.2 "manufactured by Waters," HSP gel column, HR1,3 μm,6 mm. times.150 mm ". times.2" manufactured by Waters
The measurement conditions were as follows:
column temperature: 40 deg.C
RI detector set temperature: 35 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 0.5 ml/min
Sample amount: 10 μ l
Sample concentration: 0.7 wt%
The polyvinyl acetal resin is obtained by acetalizing a polyvinyl alcohol resin with an aldehyde, for example. The aldehyde is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.
Specific examples of the phenoxy resin include FX280 and FX293 manufactured by toyoho chemical corporation, and YX8100, YL6954, and YL6974 manufactured by mitsubishi chemical corporation.
Specific examples of the polyvinyl acetal resin include S-LEC KS series manufactured by Water chemical industries, Inc., and examples of the polyamide resin include KS5000 series manufactured by Hitachi chemical Co., Ltd, and BP series manufactured by Nippon chemical Co., Ltd.
Examples of the polyamide-imide resin include KS9000 series manufactured by hitachi chemical company.
Since the thermoplastic polyhydroxypolyether resin has a high glass transition temperature and excellent heat resistance when it has a fluorene skeleton, it can maintain its glass transition temperature while maintaining a low thermal expansion coefficient based on a semi-solid or solid epoxy resin, and the resulting cured coating film has both a low thermal expansion coefficient and a high glass transition temperature in a balanced manner. In addition, since the thermoplastic polyhydroxypolyether resin has hydroxyl groups, it exhibits good adhesion to a semiconductor wafer.
The film-forming property imparting polymer component may be a block copolymer of monomers constituting the above components. A block copolymer is a copolymer in which two or more polymers having different properties are covalently bonded to form a long-chain molecular structure. As the block copolymer, X-Y-X type or X-Y-X' type block copolymers are preferable. In the X-Y-X type and X-Y-X 'type block copolymers, it is preferable that the block copolymer is composed of polymer units in which the central Y block is a soft block and has a low glass transition temperature (Tg), and the outer X or X' blocks are hard blocks and have a higher glass transition temperature (Tg) than the central Y block. The glass transition temperature (Tg) was measured by Differential Scanning Calorimetry (DSC). X and X' may be different polymer units from each other or the same polymer unit.
Further, among the X-Y-X type and X-Y-X ' type block copolymers, a block copolymer in which X or X ' includes a polymer unit having a Tg of 50 ℃ or higher and a polymer unit having a glass transition temperature (Tg) of Y of X or X ' or lower is more preferable. In the X-Y-X type and X-Y-X 'type block copolymers, X or X' is preferably highly compatible with a curable component described later, and Y is preferably less compatible with the curable component. By forming 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), it is considered that a specific structure is easily expressed in the matrix.
Among the above-mentioned various polymers, preferred are phenoxy resins, polyvinyl acetal resins, thermoplastic polyhydroxypolyether resins having a fluorene skeleton, and block copolymers.
The proportion of the film-property-imparting polymer component in the total components constituting the sealing material for a semiconductor is not particularly limited, and is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, when the total of all the components is 100 parts by mass.
< component for imparting reactive film Property to Polymer >
The component constituting the sealing material for a semiconductor may include a film-property-imparting polymer component which is reactive with a curable component, which will be described later. As such a reactive film-property imparting polymer, a carboxyl group-containing resin or a phenol resin is preferably used. In particular, the use of a carboxyl group-containing resin is preferable because it is likely to react with an epoxy resin when the resin contains an epoxy resin as a curable component, and thus the resin imparts film formability and improves the properties as a semiconductor protective film.
As the carboxyl group-containing resin, the following resins (1) to (7) can be preferably used.
Preferably, there may be used:
(1) carboxyl group-containing urethane resins obtained by addition polymerization of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing diol compounds such as dimethylolpropionic acid and dimethylolbutyric acid, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, bisphenol a alkylene oxide adduct diols, and compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group;
(2) a carboxyl group-containing urethane resin obtained by addition polymerization of a diisocyanate and a carboxyl group-containing diol compound;
(3) carboxyl group-containing resins obtained by copolymerization of unsaturated carboxylic acids such as (meth) acrylic acid with unsaturated group-containing compounds such as styrene, α -methylstyrene, lower alkyl (meth) acrylates, and isobutylene;
(4) a carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a 2-functional epoxy resin or a 2-functional oxetane resin to add a 2-membered acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting hydroxyl group;
(5) a carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin and reacting the resulting hydroxyl group with a polybasic acid anhydride;
(6) a carboxyl group-containing resin obtained by reacting a polyphenol compound, which is a compound having 2 or more phenolic hydroxyl groups in one molecule, with an alkylene oxide such as ethylene oxide or propylene oxide, and reacting the resultant reaction product such as a polyol resin with a polybasic acid anhydride; and
(7) a carboxyl group-containing resin obtained by reacting a polyphenol compound having 2 or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the resultant reaction product such as a polyol resin with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and further reacting the resultant reaction product with a polybasic acid anhydride; and the like. In the present specification, the term (meth) acrylate refers to acrylate, methacrylate and a mixture thereof.
Among the above 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 them, the resins (6) and (7) are preferable because of their good balance of all properties.
The weight average molecular weight of the reactive film-property imparting polymer differs depending on the resin skeleton, and is usually preferably 2X 103～1.5×105More preferably 3X 10, in the above range3～1×105But is not limited to these ranges.
The proportion of the reactive film-property imparting polymer component in the entire components constituting the sealing material for a semiconductor is not particularly limited, and for example, it is preferable to replace 20 to 60 parts by mass of 100 parts by mass of the film-property imparting polymer with the reactive film-property imparting polymer.
< other ingredients >
In addition to the above components, various additives may be blended as necessary in the sealing material for a semiconductor of the present invention. Examples of the various additives include a leveling agent, a plasticizer, an ion scavenger, a getter, a chain transfer agent, and a releasing agent. Among them, a flame retardant such as antimony trioxide can be blended within a range that does not impair the characteristics, and it is preferable that the flame retardant such as antimony trioxide is not substantially contained from the viewpoint of environmental load.
The thickness of the sealing material for a semiconductor 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, and is preferably 3 to 800 μm, more preferably 5 to 700 μm, and particularly preferably 7 to 600 μm.
The semiconductor sealing material of the present invention may have a single-layer structure or a multilayer structure.
The maximum transmittance of the sealing material for a semiconductor of the present invention at a wavelength of 300nm to 1200nm, which is a standard for expressing the transmittance of at least one of visible light, infrared light, and ultraviolet light, is preferably 20% or less, more preferably 0 to 15%, further preferably more than 0% and 10% or less, and particularly preferably 0.001% to 8%. By setting the maximum transmittance of the sealing material for a semiconductor at a wavelength of 300nm to 1200nm to the above range, the transmittance in at least one of the visible light wavelength region and the infrared wavelength region is reduced, and effects such as prevention of an operation failure due to infrared rays of the semiconductor device and improvement of visibility of printed characters can be obtained. The maximum transmittance of the sealing material for a semiconductor at a wavelength of 300nm to 1200nm can be adjusted by the kind and content of the colorant component. In the present specification, the maximum transmittance of the sealing material for a semiconductor means: the total light transmittance of the cured semiconductor sealing material (thickness: 25 μm) at 300nm to 1200nm was measured by a UV-vis spectrometer (manufactured by Shimadzu corporation), and the maximum transmittance was defined as the value at which the transmittance was the highest (maximum transmittance).
The semiconductor sealing material of the present invention may be in any form of liquid, granular, flat plate, and sheet, and is preferably in a sheet form because it can be handled easily.
< method for producing sealing Material for semiconductor >
The semiconductor sealing material of the present invention is obtained by using a composition (mixture) obtained by mixing the above components at a predetermined ratio. The composition may be diluted with a solvent in advance, or may be added to a solvent at the time of mixing. When the composition is used to produce a sealing material for a semiconductor, the composition may be diluted with a solvent. Examples of the solvent include ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, cyclohexane, toluene, and heptane. This method can be used to obtain a liquid semiconductor sealing material.
The sheet-like sealing material for semiconductors can be prepared by applying the composition (mixture) prepared as described above to a support to form a film. As the film forming method, a conventionally known method can be applied, and the composition (mixture) is applied to a support by a known means such as a flat press method, a roll knife coater, a gravure coater, a die coater, or a reverse coater, and dried, thereby obtaining a sealing material for a semiconductor. Further, by adjusting the amount of the composition (mixture) applied, a semiconductor sealing material having the above thickness can be obtained.
As a support, the input device preferably comprises a release paper (セパレート), a release film, a release paper (セパ), a release film, a release paper, etc. Further, a support having a release layer formed on one or both surfaces of a release paper (i-type) substrate composed of a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as oriented polypropylene (OPP), or a plastic film such as a polyimide film may be used. The release layer is not particularly limited as long as it is a material having releasing property, and examples thereof include silicone resin, organic resin-modified silicone resin, and fluororesin.
The sealing material for a semiconductor of the present invention can also be used as a sealing material for a printed circuit board, a sealing material for a solar cell material, and an adhesive for a sealing material substrate for a wire/cable and a semiconductor chip. In particular, the sealing material for a semiconductor of the present invention is preferably used for a fan-out wafer level package including a semiconductor chip, a sealing material for a semiconductor in which the semiconductor chip is embedded so that a circuit formation surface of the semiconductor chip is exposed on a surface thereof, and a rewiring layer provided on the circuit formation surface side of the semiconductor chip, the rewiring layer also being provided in a region of the sealing material for a semiconductor other than a semiconductor chip region.
Examples
The present invention will be described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means part by mass.
< Synthesis of reactive film Property-imparting Polymer (carboxyl group-containing resin) 1 >
120.0g of bisphenol A-formaldehyde type phenol resin (product name "BPA-D" manufactured by KANGSHUKI CO., LTD., OH equivalent: 120), 1.20g of potassium hydroxide and 120.0g of toluene were put into an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device, and the inside of the system was replaced with nitrogen gas under stirring to heat the system. Then, 63.8g of propylene oxide was slowly dropped at 125 to 132 ℃ at a rate of 0 to 4.8kg/cm2The reaction was carried out for 16 hours.
Thereafter, the reaction solution was cooled to room temperature, and 1.56g of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide, thereby obtaining a propylene oxide reaction solution of a bisphenol A-formaldehyde type phenol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2g/eq. The epoxy resin composition was prepared by adding 1.08 moles of alkylene oxide to 1 equivalent of phenolic hydroxyl group on average.
293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene 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 to react at 110 ℃ for 12 hours under stirring.
The water produced by the reaction was distilled off as an azeotropic mixture with toluene to give 12.6 g. After that, the reaction solution was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Thereafter, the toluene was replaced with 118.1g of propylene glycol monomethyl ether acetate in an evaporator and simultaneously distilled off to obtain a novolak-type acrylate resin solution.
Next, 332.5g of the obtained novolak type acrylate resin solution and 1.22g of triphenylphosphine were put into a reactor equipped with a stirrer, a thermometer and an air blowing tube, air was blown at a rate of 10 ml/min, 60.8g of tetrahydrophthalic anhydride was slowly added under stirring, and the mixture was reacted at 95 to 101 ℃ with stirringAfter 6 hours, a reactive film-forming property imparting polymer (carboxyl group-containing resin) 1 having an acid value of solid matter of 88mgKOH/g and a nonvolatile matter of 71% was obtained. This was used as a resin solution A. The weight average molecular weight of the reactive film-forming property imparting polymer (carboxyl group-containing resin) 1 component contained in the resin solution A was 4X 103。
The weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) method (polystyrene standard) using the following measurement apparatus and measurement conditions.
A measuring device: waters manufactures "Waters 2695"
A detector: waters manufactures "Waters 2414", RI (differential refractometer)
Column: "HSP gel column, HR MB-L,3 μm,6 mm. times.150 mm". times.2 "manufactured by Waters," HSP gel column, HR1,3 μm,6 mm. times.150 mm ". times.2" manufactured by Waters
The measurement conditions were as follows:
column temperature: 40 deg.C
RI detector set temperature: 35 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 0.5 ml/min
Sample amount: 10 μ l
Sample concentration: 0.7 wt%
< production of sealing Material 1 for semiconductor >
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%.
The sealing material composition solution 1 was applied to a polyethylene terephthalate film (PET film) whose surface was subjected to a peeling treatment, and dried at 100 ℃ for 10 minutes to prepare a sealing material 1 for a semiconductor having a thickness of 50 μm. The films were laminated into 6 sheets to prepare a sealing material 1 for a semiconductor having a thickness of 300. mu.m.
< preparation of sealing Material 2 for semiconductor >
The following components were mixed, heated at 70 ℃ for 4 minutes and then at 120 ℃ for 6 minutes using a roll mill, and the total of the mixture was reduced in pressure (0.01 kg/cm) for 10 minutes2) The resulting mixture was melt-kneaded to prepare a kneaded product 2.
The obtained kneaded material 2 was arranged so as to be sandwiched between two 50 μm cover films (pu rex films), and the kneaded material was formed into a sheet by a flat press method, thereby obtaining a sheet-like sealing material 2 for a semiconductor having a thickness of 300 μm.
< preparation of sealing Material 3 for semiconductor >
The following components were mixed, heated at 70 ℃ for 4 minutes and then at 120 ℃ for 6 minutes using a roll mill, and the total of the mixture was reduced in pressure (0.01 kg/cm) for 10 minutes2) The resulting mixture was melt-kneaded to prepare a kneaded product 3.
The obtained kneaded material 3 was arranged so as to be sandwiched between two 50 μm PET films (Purex films), and the kneaded material was formed into a sheet by a flat press method, whereby a sheet-like sealing material 3 for a semiconductor having a thickness of 300 μm was obtained.
< preparation of sealing Material 4 for semiconductor >
The following components were mixed, heated at 70 ℃ for 4 minutes and then at 120 ℃ for 6 minutes using a roll mill, and the total of the mixture was reduced in pressure (0.01 kg/cm) for 10 minutes2) The resulting mixture was melt-kneaded to prepare a kneaded product 4.
The obtained kneaded material 4 was disposed so as to be sandwiched between two 50 μm cover films (pu rex films), and the kneaded material was formed into a sheet by a flat press method, thereby obtaining a sheet-like sealing material 4 for a semiconductor having a thickness of 300 μm.
< production of sealing Material 5 for semiconductor >
The following components were mixed, heated at 70 ℃ for 4 minutes and then at 120 ℃ for 6 minutes using a roll mill, and the total of the mixture was reduced in pressure (0.01 kg/cm) for 10 minutes2) The resulting mixture was melt-kneaded to prepare a kneaded product 5.
In the semiconductor sealing material 5, assuming that the number of moles of the functional group of anthraquinone as the oxidizing agent is 100%, the number of moles of the functional group of the antioxidant is about 12%.
The obtained kneaded material 5 was disposed so as to be sandwiched between two 50 μm cover films (pu rex films), and the kneaded material was formed into a sheet by a flat press method, thereby obtaining a sheet-like sealing material 5 for a semiconductor having a thickness of 300 μm.
< production of sealing Material 6 for semiconductor >
A semiconductor sealing material 6 having a thickness of 300 μm was produced in the same manner as the semiconductor sealing material 1 except that anthraquinone was not used.
< production of sealing Material 7 for semiconductor >
A sealant 7 for a semiconductor having a thickness of 300 μm was produced in the same manner as the sealant 2 for a semiconductor except that anthraquinone was not used.
< production of sealing Material 8 for semiconductor >
A semiconductor sealing material 8 having a thickness of 300 μm was produced in the same manner as the semiconductor sealing material 3 except that manganese dioxide was not used.
< production of sealing Material 9 for semiconductor >
A sealant 9 for a semiconductor having a thickness of 300 μm was produced in the same manner as the sealant 4 for a semiconductor except that benzoyl peroxide was not used.
< production of sealing Material 10 for semiconductor >
A sealant 10 for a semiconductor was produced in the same manner as the sealant 5 for a semiconductor except that anthraquinone and ADKSTAAO-60 were not used, and had a thickness of 300. mu.m.
< preparation of semiconductor wafer >
As a semiconductor wafer, a wafer manufactured by Canosis co., ltd. and having 100nm of SiO formed on one surface thereof was prepared2A film, 4 inch, P-type silicon wafer ground to a thickness of 200 μm.
< manufacture of semiconductor Package >
The semiconductor wafer was diced using a dicing apparatus to obtain semiconductor chips of 10mm × 10mm square. Disposing a temporary fixing film on the SUS planar substrate according to SiO2The semiconductor chip is further disposed so that the surface thereof is in contact with the temporary fixing film. A sealing material for a semiconductor having a 20mm × 20mm square shape was laminated thereon, the center position was roughly matched, and compression molding was performed at 150 ℃ for 1 hour by a heating press-bonding machine. The temporary fixing film is peeled off from the obtained laminate to obtain a semiconductor package.
As a confirmation method for suppressing formation of a gap between the semiconductor chip and the sealing material for semiconductor, adhesion was evaluated. The evaluation was performed as follows.
< evaluation >
TMAH 2.38% aqueous solution (trade name: AD-10, manufactured by Moore chemical industries, Ltd.) was prepared at 25 ℃ and the semiconductor package thus prepared was immersed in the aqueous solution to prepare a SiO layer on the semiconductor chip2Face up, for 5 minutes. After that, the semiconductor package was taken out and rinsed 2 times with pure water. Thereafter, moisture was blown off by air blowing, and the sheet was left on a heating plate set at 100 ℃ for 5 minutes and recovered. For the resulting processed semiconductorAnd a package in which a boundary portion between the semiconductor chip and the sealing material is observed from the semiconductor chip side by an optical microscope and an electron microscope, and a case where the sealing material is adhered without generating a gap is judged to be good, and a case where the sealing material is observed is judged to be poor. The evaluation results are shown in table 1 below.
[ Table 1]
| Sealing material for semiconductor | Adhesion Property | |
| Example 1 | Sealing material for semiconductor 1 | ○ |
| Example 2 | Sealing material 2 for semiconductor | ○ |
| Example 3 | Sealing material 3 for semiconductor | ○ |
| Example 4 | Sealing material 4 for semiconductor | ○ |
| Example 5 | Sealing material 5 for semiconductor | ○ |
| Comparative example 1 | Semiconductor sealing material 6 | × |
| Comparative example 2 | Sealing material 7 for semiconductor | × |
| Comparative example 3 | Sealing material 8 for semiconductor | × |
| Comparative example 4 | Sealing material 9 for semiconductor | × |
| Comparative example 5 | Sealing material 10 for semiconductor | × |
From the evaluation results shown in table 1, it is clear that examples 1 to 5 using the sealing material for a semiconductor containing an oxidizing agent are excellent in adhesion between the semiconductor chip and the sealing material even when subjected to alkali treatment. On the other hand, in comparative examples 1 to 5 using the semiconductor sealing material containing no oxidant, a gap was formed at the boundary between the semiconductor chip and the sealing material by the alkali treatment. Although presumed, it is believed that: in the semiconductor wafers of examples 1 to 5, the surface of Si as the semiconductor chip was oxidized by the oxidizing agent contained in the sealing material for semiconductor to form a film containing SiO2As a result, etching of the side surface of the semiconductor chip due to the alkali treatment is suppressed.
Claims (5)
1. A sealing material for a semiconductor, comprising a curable component and an organic oxidizing agent capable of oxidizing a semiconductor, wherein the curable component comprises an epoxy resin having a total content of chlorine and bromine of 3000ppm or less.
2. The sealing material for semiconductors according to claim 1, further comprising a curing agent component, a curing accelerator component and an inorganic filler.
3. The sealing material for semiconductors according to claim 1, which has a sheet-like shape.
4. The sealing material for semiconductors according to claim 1, which is used for a fan-out type wafer level package.
5. The sealing material for semiconductors according to claim 1, wherein the organic oxidizing agent is at least one selected from the group consisting of hydrogen peroxides, quinones, pyridines, organic nitro compounds, m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, performic acid, benzoyl peroxide, diethyl peroxide, and diacetyl peroxide.
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| JP2015254480A JP5978380B1 (en) | 2015-12-25 | 2015-12-25 | Sealant for semiconductor |
| PCT/JP2016/088444 WO2017111057A1 (en) | 2015-12-25 | 2016-12-22 | Sealant for semiconductor |
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| JP2000109543A (en) * | 1998-10-07 | 2000-04-18 | Hitachi Chem Co Ltd | Epoxy resin composition for semiconductor sealing use and semiconductor device using the same |
| WO2015037458A1 (en) * | 2013-09-12 | 2015-03-19 | 日東電工株式会社 | Method for manufacturing semiconductor device |
| WO2015098842A1 (en) * | 2013-12-26 | 2015-07-02 | 日東電工株式会社 | Method for manufacturing semiconductor device |
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| JP3128291B2 (en) * | 1990-10-31 | 2001-01-29 | 株式会社東芝 | Maleimide resin composition and resin-sealed semiconductor device using the same |
| JP2000036552A (en) * | 1998-07-17 | 2000-02-02 | Fujitsu Ltd | Semiconductor device and separately taking out method of metal component in sealing material used therein |
| US20060009547A1 (en) * | 2002-09-05 | 2006-01-12 | Hisashi Maeshima | Process for preparation of alicyclic diepoxy compound, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| JP3998564B2 (en) * | 2002-11-13 | 2007-10-31 | 株式会社巴川製紙所 | Curable adhesive composition for semiconductor encapsulation and adhesive sheet |
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| KR101393700B1 (en) * | 2012-11-29 | 2014-05-13 | 서울과학기술대학교 산학협력단 | Manufacturing of fan-out wafer level packaging fortified preventing warpage of wafer |
| JP2015041663A (en) * | 2013-08-21 | 2015-03-02 | 日東電工株式会社 | Sealing sheet, and method of manufacturing semiconductor device |
| JP2015056458A (en) * | 2013-09-10 | 2015-03-23 | 株式会社東芝 | Semiconductor device |
| JP6546378B2 (en) * | 2013-11-19 | 2019-07-17 | 日東電工株式会社 | Resin sheet |
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| JP2000109543A (en) * | 1998-10-07 | 2000-04-18 | Hitachi Chem Co Ltd | Epoxy resin composition for semiconductor sealing use and semiconductor device using the same |
| WO2015037458A1 (en) * | 2013-09-12 | 2015-03-19 | 日東電工株式会社 | Method for manufacturing semiconductor device |
| WO2015098842A1 (en) * | 2013-12-26 | 2015-07-02 | 日東電工株式会社 | Method for manufacturing semiconductor device |
Also Published As
| Publication number | Publication date |
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| TW201737429A (en) | 2017-10-16 |
| JP2017118045A (en) | 2017-06-29 |
| CN108369928A (en) | 2018-08-03 |
| JP5978380B1 (en) | 2016-08-24 |
| MY196462A (en) | 2023-04-12 |
| TWI750145B (en) | 2021-12-21 |
| PH12018501308A1 (en) | 2019-02-11 |
| KR20180098558A (en) | 2018-09-04 |
| KR102384582B1 (en) | 2022-04-08 |
| WO2017111057A1 (en) | 2017-06-29 |
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