TW201546167A - Resin composition for encapsulation and semiconductor device - Google Patents

Abstract

A sealing resin composition used for sealing a semiconductor element and bonding wire, which is connected to said semiconductor element and has Cu as the main component. The sealing resin composition comprises an epoxy resin and a curing agent and the difference (pH(1) - pH(2)) between pH(1) that is measured under Condition 1 and pH(2) that is measured under Condition 2 is 1.1 or less.

Description

Sealing resin composition, and semiconductor device

The present invention relates to a resin composition for sealing and a semiconductor device.

In order to improve the reliability of a semiconductor device having a bonding wire, various studies have been conducted on a resin composition for sealing. As such a technique, for example, those described in Patent Document 1 can be cited.

Patent Document 1 describes an epoxy resin composition for semiconductor encapsulation containing a biphenyl type epoxy resin having a hydrolyzable chlorine content of 10 to 20 ppm.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-67694

The present invention seeks to improve the semiconductor by curing a resin composition for sealing The reliability of a device and a semiconductor device in which a bonding wire connected to a semiconductor element and containing Cu as a main component is sealed.

According to the present invention, there is provided a resin composition for sealing, which is used for sealing a semiconductor element and a bonding wire which is connected to the semiconductor element and contains Cu as a main component; and contains an epoxy resin and a curing agent; The difference between pH ₍₁₎ measured under Condition 1 and pH ₍₂₎ measured under Condition 2 below (pH _{(1) -} pH ₍₂₎ ) was 1.1 or less.

(Condition 1: The cured product obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, 5 g of the pulverized material immediately after pulverization was placed in 50 ml of pure water. After the middle part, the pure water is subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH of the obtained extract (pH ₍₁₎ ) is measured)

(Condition 2: The cured product obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, the pulverized product was stored at 175 ° C for 500 hours. Then, 5 g of the pulverized material after storage was placed in 50 ml of pure water, and then the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH ₍₂₎ ) of the obtained extract was measured.

According to the present invention, there is provided a semiconductor device comprising: a semiconductor element; and a bonding wire connected to the semiconductor element and having Cu as a main component; The sealing resin is composed of a cured product of the sealing resin composition, and seals the semiconductor element and the bonding wire.

According to the present invention, the reliability of the semiconductor device can be improved.

10‧‧‧Grain Adhesive

20‧‧‧Semiconductor components

22‧‧‧electrode pads

30‧‧‧Substrate

32‧‧‧crystal seat

34‧‧‧External leads

40‧‧‧bonding line

50‧‧‧ sealing resin

100‧‧‧Semiconductor device

The above and other objects, features, and advantages of the invention will be apparent from the appended claims appended claims

Fig. 1 is a cross-sectional view showing the semiconductor device of the embodiment.

Hereinafter, the form of the implementation will be described using the drawings. In the drawings, the same components are denoted by the same reference numerals, and the description is omitted as appropriate.

Fig. 1 is a cross-sectional view showing a semiconductor device 100 of the present embodiment.

The sealing resin composition of the present embodiment is for sealing a semiconductor element and a bonding wire which is connected to the semiconductor element and contains Cu as a main component, and contains an epoxy resin and a curing agent. Further, the difference between the pH ₍₁₎ measured under the following condition 1 and the pH ₍₂₎ measured under the following condition 2 (pH _{(1) -} pH ₍₂₎ ) was 1.1 or less.

(Condition 1: The cured product obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, 5 g of the pulverized material immediately after pulverization was placed in 50 ml of pure water. After the middle part, the pure water is subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH of the obtained extract (pH ₍₁₎ ) is measured)

(Condition 2: The cured product obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, the pulverized product was stored at 175 ° C for 500 hours. Then, 5 g of the pulverized material after storage was placed in 50 ml of pure water, and then the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH ₍₂₎ ) of the obtained extract was measured.

One of the indexes indicating the reliability of the semiconductor device is high temperature storage characteristics. The high-temperature storage characteristics can be evaluated, for example, based on the connectivity of the connection portion of the bonding wire and the semiconductor element mainly composed of Cu in a high-temperature environment. However, for example, when stored at a high temperature for a long time of 1000 hours, it is difficult to maintain good connectivity between the bonding wires and the semiconductor elements. Therefore, it is desired to further improve the high-temperature storage characteristics so that good connectivity can be maintained even when stored at a high temperature for a long period of time.

The present inventors conducted an effort to study a sealing resin composition capable of improving high-temperature storage characteristics. As a result, there was a new discovery that high temperature storage can be achieved by controlling the difference between pH ₍₁₎ measured under the above condition 1 and pH ₍₂₎ measured under the above condition 2 (pH _{(1) -} pH ₍₂₎ ). Improvement in features. In the present embodiment, a sealing resin composition having a pH _{(1) -} pH ₍₂ ) of 1.1 or less is realized based on such a finding. Thereby, the high-temperature storage characteristics of the semiconductor device manufactured using the resin composition for sealing can be improved. Therefore, the reliability of the semiconductor device can be improved.

In the following, the semiconductor device 100 including the sealing resin composition of the present embodiment and the sealing resin 50 including the cured product of the sealing resin composition will be described in detail.

First, the resin composition for sealing will be described.

The sealing resin composition is used to seal a semiconductor element and a bonding wire which is connected to the semiconductor element and contains Cu as a main component. In the present embodiment, a case where the resin for sealing is used is exemplified A sealing resin composed of a cured product of the composition seals the semiconductor element and the bonding wire, thereby forming a semiconductor package.

The semiconductor element is mounted, for example, on a substrate such as a crystal frame or an organic substrate constituting the lead frame or another semiconductor element. At this time, the semiconductor element is electrically connected to a lead wire, an organic substrate, or another semiconductor element constituting the lead frame via a bonding wire. The bonding wire is connected, for example, to an electrode pad provided on the semiconductor element. The electrode pad of the semiconductor element is composed of, for example, a metal material having at least Al on its surface as a main component.

The bonding wires are composed of a metal material mainly composed of Cu. Examples of such a metal material include a metal material composed of a simple substance of Cu or an alloy material containing Cu as a main component and containing other metals.

In the present embodiment, a bonding wire composed of a metal material having a Cu content of 99.9% by mass or more is used as an example of a preferable aspect from the viewpoint of cost reduction. In general, when such a Cu wire is used, there is a concern that it is difficult to improve the high-temperature storage characteristics of the semiconductor device. However, according to the present embodiment, by controlling (pH _{(1) -} pH ₍₂₎ ) as follows, excellent high-temperature storage characteristics can be achieved even when the Cu wire as described above is used.

The difference between the pH ₍₁₎ measured under the following condition 1 and the pH ₍₂₎ measured under the following condition 2 (pH _{(1) -} pH ₍₂₎ ) was 1.1 or less. Thereby, as described above, the high-temperature storage characteristics of the semiconductor device can be improved.

(Condition 1)

The cured resin composition obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, 5 g of the pulverized material immediately after the pulverization was placed in 50 ml of pure water, and then the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH of the obtained extract (pH _{(1) was} measured. ₎ ).

(Condition 2)

The cured resin composition obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized to obtain a pulverized product. Then, the pulverized product was stored at 175 ° C for 500 hours. Then, 5 g of the pulverized material after storage was placed in 50 ml of pure water, and then the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH of the obtained extract (pH _{(2) was} measured. ).

In the above conditions 1 and 2, the pulverization treatment of the cured product can be carried out, for example, by using TI-100 (manufactured by CMT Co., Ltd.) and 5.2 g of the cured product in a pulverizer for 2 minutes. Moreover, in the above-mentioned condition 1 and the above-mentioned condition 2, the hot water extraction treatment can be carried out, for example, using a pressure vessel made of a polytetrafluoroethylene inner container and a metal outer container. Moreover, in the above-mentioned condition 2, the storage of the pulverized material is not particularly limited, and for example, it can be carried out by placing a sealed container in which the resin composition for sealing is placed in a dust-free oven maintained at a temperature of 175 °C.

From the viewpoint of more effectively improving the high-temperature storage characteristics of the semiconductor device, (pH _{(1) -} pH ₍₂₎ ) is preferably 0.8 or less, and particularly preferably 0.6 or less. The lower limit of (pH _{(1) -} pH ₍₂₎ ) is not particularly limited, and can be, for example, 0.1.

In the present embodiment, the pH ₍₁₎ measured by the above condition 1 of the resin composition for sealing is preferably 5 or more and 7 or less, more preferably 5 or more and 6.5 or less. Thereby, the balance of the characteristics required for the sealing resin composition such as the high-temperature storage property or the reflow resistance can be more effectively improved. Therefore, it is also possible to contribute to the improvement of the reliability of the semiconductor device obtained by using the resin composition for sealing.

In the present embodiment, the pH ₍₁₎ , pH _(2), and (pH _{(1) -} pH ₍₂₎ ) of the resin composition for sealing can be adjusted, for example, by appropriately adjusting the components contained in the resin composition for sealing. The type or content, the preparation method of the resin composition for sealing, and the like are controlled. As an example of the preparation method of the resin composition for sealing, the surface treatment by the coupling agent (D) with respect to the filler (C) is mentioned below.

The resin composition for sealing contains an epoxy resin (A) and a hardener (B). Thereby, a sealing resin for sealing the bonding wires and the semiconductor element can be formed using the sealing resin composition.

((A) epoxy resin)

The epoxy resin (A) can be used for all monomers, oligomers, and polymers having two or more epoxy groups in one molecule, and the molecular weight or molecular structure thereof is not particularly limited.

In the present embodiment, the epoxy resin (A) may contain, for example, a biphenyl type epoxy resin; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a tetramethyl bisphenol F type epoxy resin. Bisphenol type epoxy resin; bismuth type epoxy resin; phenol novolak type epoxy resin, phenol novolac type epoxy resin and other novolak type epoxy resin; trisphenol methane type epoxy resin, alkyl modification A polyfunctional epoxy resin such as a trisphenol methane type epoxy resin; a phenol aralkyl type epoxy resin having a phenyl group skeleton; and an aralkyl type ring such as a phenol aralkyl type epoxy resin having a stretched phenyl skeleton; Oxygen resin; dihydroxynaphthalene type epoxy resin; naphthalene type epoxy resin such as epoxy resin obtained by etherification of dihydroxynaphthalene dimer glycidyl; triglycidyl isocyanurate, monoallyl Diglycidyl isocyanurate, etc. One or more of a modified epoxy resin compound such as a core epoxy resin; a dicyclopentadiene-modified phenol type epoxy resin; Among these, it is more preferable to contain one or two or more kinds of a naphthalene type epoxy resin, an aralkyl type epoxy resin, and a biphenyl type epoxy resin, and it is especially preferable to contain an aralkyl type epoxy resin. Further, a bisphenol type epoxy ring such as an aralkyl type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a tetramethyl bisphenol F type epoxy resin The oxygen resin and the fluorene type epoxy resin preferably have crystallinity.

More preferably, the epoxy resin (A) is an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2), which is represented by the following formula (3). At least one of a group consisting of an epoxy resin and an epoxy resin represented by the following formula (4). In the above, it is particularly preferable to use an epoxy resin represented by the following formula (1), an epoxy resin represented by the following formula (2), and an epoxy resin represented by the following formula (4). At least one kind.

(In the formula (1), Ar ¹ represents a phenyl or anthracene group, and in the case where Ar ¹ is a naphthyl group, the glycidyl ether group may be bonded to any of the α-position and the β-position. Ar ² Represents any of a phenyl, a phenyl or a naphthyl group. R _a and R _b each independently represent a hydrocarbon group having 1 to 10 carbon atoms. g is an integer from 0 to 5, and h is an integer from 0 to 8. n ³ represents the degree of polymerization, and the average value is 1~3)

(In the formula (2), a plurality of R _c existing independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n ⁵ represents a degree of polymerization, and the average value thereof is 0 to 4)

(In the formula (3), a plurality of R _d and R _{e present} independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n ⁶ represents a degree of polymerization, and the average value thereof is 0 to 4)

(In the formula (4), R _f each independently represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R _g each independently represents a hydrocarbon group having 1 to 4 carbon atoms. a and b are integers of 0 or 1, and c is 0 to 5 Integer)

The content of the epoxy resin (A) in the resin composition for sealing is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more based on the entire resin composition for sealing. When the content of the epoxy resin (A) is at least the above lower limit value, the fluidity of the resin composition for sealing can be improved. Further, it is possible to more reliably suppress breakage of the bonding wire due to an increase in viscosity of the resin composition for sealing. On the other hand, the content of the epoxy resin (A) in the resin composition for sealing is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass based on the entire resin composition for sealing. the following. By setting the content of the epoxy resin (A) to be equal to or lower than the above upper limit value, the moisture resistance reliability or the reflow resistance of the semiconductor device can be improved.

((B) hardener)

The curing agent (B) contained in the resin composition for sealing can be roughly classified into, for example, an addition polymerization type curing agent, a catalyst type curing agent, and a condensation type curing agent.

Examples of the addition polymerization type curing agent used as the curing agent (B) include di-ethyltriamine (DETA), tri-ethyltetramine (TETA), m-xylylenediamine (MXDA), and the like. Aromatic polyamines such as aliphatic polyamines, diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenyl hydrazine (DDS), and dicyandiamide (DICY), organic two Polyamine compounds such as hydrazine; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic acid An anhydride such as a dianhydride (PMDA) or a benzophenone tetracarboxylic acid (BTDA); a phenolic resin such as a novolak type phenol resin or a polyvinyl phenol; a polysulfide, a thioester, and a sulfur; a polythiol compound such as an ether; an isocyanate compound such as an isocyanate prepolymer or a blocked isocyanate; an organic acid such as a carboxylic acid-containing polyester resin.

Examples of the catalyst-type hardener used for the hardener (B) include three grades such as dimethylbenzylamine (BDMA) and 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30). An amine compound; an imidazole compound such as 2-methylimidazole or 2-ethyl-4-methylimidazole (EMI24); a Lewis acid such as a BF3 complex or the like.

Examples of the condensing type hardening agent used for the curing agent (B) include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; a melamine resin such as a hydroxymethyl group-containing melamine resin.

Among these, a phenol resin-based curing agent is preferred from the viewpoint of improving the balance between flame resistance, moisture resistance, electrical properties, curability, and storage stability. Hardened as a phenol resin The agent can be used for all monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited.

The phenol resin-based curing agent used as the curing agent (B) may, for example, contain a novolac type resin selected from the group consisting of a phenol novolak resin, a cresol novolak resin, and a bisphenol novolak resin; polyvinylphenol; trisphenol methane phenol; a polyfunctional phenol resin such as a resin; a modified phenol resin such as a terpene-modified phenol resin or a dicyclopentadiene-modified phenol resin; a phenol aralkyl resin having a phenyl group skeleton and/or a stretched phenyl skeleton; An aralkyl type resin such as a naphthol aralkyl resin having a phenyl group and/or a pendant phenyl skeleton; or one or more selected from the group consisting of bisphenol A and a bisphenol compound such as bisphenol F. Among these, it is preferable to contain at least one of an aralkyl type resin and a polyfunctional phenol resin from the viewpoint of improving the balance between reflow resistance and high temperature storage characteristics.

The curing agent (B) is preferably at least one curing agent containing a group selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6).

(In the formula (5), Ar ³ represents a phenyl or a naphthyl group, and in the case where Ar ³ is a naphthyl group, the hydroxy group may be bonded to any of the α-position and the β-position. Ar ⁴ represents a benzene extension. Any of a group of a phenyl group or a phenylene group. R ⁿ and R ^m each independently represent a hydrocarbon group having 1 to 10 carbon atoms. i is an integer of 0 to 5, and j is an integer of 0 to 8. n ⁴ Indicates the degree of polymerization, the average value is 1~3)

(In the formula (6), a plurality of R _h existing independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n ⁸ represents a degree of polymerization, and the average value thereof is 0 to 4)

The content of the curing agent (B) in the resin composition for sealing is preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 4% by mass or more based on the entire resin composition for sealing. By setting the content of the curing agent (B) to be equal to or higher than the above lower limit value, it is possible to realize a sealing resin composition having sufficient fluidity, and it is possible to improve moldability. On the other hand, the content of the curing agent (B) in the resin composition for sealing is preferably 15% by mass or less, more preferably 13% by mass or less, and particularly preferably 11% by mass or less based on the entire resin composition for sealing. . By setting the content of the curing agent (B) to be equal to or lower than the above upper limit value, the moisture resistance reliability or the reflow resistance of the semiconductor device can be improved.

((C) filler)

The resin composition for sealing may further contain a filler (C), for example. As the filler (C), a general semiconductor sealing epoxy resin composition can be used, and examples thereof include molten spherical cerium oxide, melt pulverized cerium oxide, crystalline cerium oxide, talc, and aluminum oxide. An inorganic filler such as titanium white or tantalum nitride; an organic filler such as an organic polyoxynium powder or a polyethylene powder. Of these, it is especially preferred to use molten spherical ceria. These fillers may be used alone or in combination of two or more.

In addition, the shape of the filler (C) is not particularly limited, and from the viewpoint of suppressing an increase in the melt viscosity of the resin composition for sealing and increasing the content of the filler, it is preferably as spherical as possible. And the particle size distribution is wider.

The content of the filler (C) in the resin composition for sealing is preferably 35 mass% or more, more preferably 50 mass% or more, and still more preferably 65 mass% or more, based on the entire resin composition for sealing. When the content of the filler (C) is at least the above lower limit value, the low moisture absorption property and the low thermal expansion property can be improved, and the moisture resistance reliability or the reflow resistance can be more effectively improved. On the other hand, the content of the filler (C) in the resin composition for sealing is preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 90% by mass or less. When the content of the filler (C) is at most the above upper limit value, it is possible to suppress a decrease in moldability due to a decrease in fluidity of the resin composition for sealing or a bonding line deviation due to high viscosity. Move and so on.

((D) coupling agent)

The surface treatment may be carried out on the filler (C) using a coupling agent (D). As the coupling agent (D), for example, various decane-based compounds such as epoxy decane, decyl decane, amino decane, alkyl decane, ureido decane, vinyl decane, methacryl decyl decane, titanium compound, and aluminum can be used. Known coupling agents such as chelate compounds and aluminum/zirconium compounds. If these are exemplified, vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-methyl propylene醯-methoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyl Triethoxy decane, γ-glycidoxypropyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl Triethoxy decane, vinyl triethoxy decane, γ-mercaptopropyl trimethoxy decane, γ-Aminopropyltriethoxydecane, γ-anilinopropyltrimethoxydecane, γ-anilinopropylmethyldimethoxydecane, γ-[bis(β-hydroxyethyl)]amine Propyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethyl Oxydecane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-(β- Aminoethyl)aminopropyldimethoxymethylnonane, N-(trimethoxydecylpropyl)ethylenediamine, N-(dimethoxymethyldecylisopropyl)ethylenediamine , methyltrimethoxydecane, dimethyldimethoxydecane, methyltriethoxydecane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxy Baseline, γ-chloropropyltrimethoxydecane, hexamethyldioxane, vinyltrimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, 3-isocyanatepropyltriethoxydecane a hydrolyzate such as 3-propenyloxypropyltrimethoxydecane or 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine System coupling agent; isopropyl triisostearate isopropyl titanate, tris(dioctylpyridinium oxy) isopropyl titanate, tris(N-aminoethyl-aminoethyl) titanate Propyl ester, bis(di-tridecylphosphite) tetraoctyl titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl) Phosphonic titanate, bis(dioctylpyridyloxy)glycolic acid titanate, bis(dioctylpyridylphosphoniumoxy) titanate, isopropyl triisodecyl titanate Ester, isopropyl methacrylate isostearyl isopropyl titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, isopropyl isostearyl decyl decyl titanate , tris(dioctylphosphite) isopropyl titanate, isopropyl tris(isopropylphenylphenyl) titanate, bis(dioctylphosphonium oxy) titanate A titanate coupling agent. These may be used alone or in combination of two or more. Among these, a decane-based compound such as epoxy decane, decyl decane, amino decane, alkyl decane, ureido decane or vinyl decane is more preferable. Moreover, in terms of improving the reliability of a semiconductor device such as reflow resistance, It is especially preferred to use decyl decane.

The surface treatment by the coupling agent (C) with the coupling agent (D) can be carried out, for example, in the following manner. First, after the filler (C) is put into a stirrer, stirring is started, and the coupling agent (D) is further added thereto, followed by stirring for 1 to 5 minutes to obtain a mixture of the filler (C) and the coupling agent (D). Then, the mixture was taken out from the mixer and allowed to stand. The standing time can be appropriately selected, and for example, it can be set to 3 minutes to 1 hour. Thereby, the filler (C) surface-treated by the coupling agent (D) can be obtained. Further, the filler (C) after the standing treatment may be further subjected to heat treatment. The heat treatment can be carried out, for example, at 30 to 80 ° C for 0.1 to 10 hours. Further, in the present embodiment, the filler (C) and the coupling agent may be obtained by stirring the filler (C) with a spray atomizing agent (D) facing the filler (C) in the mixer. a mixture of D). As the atomizer, for example, a device capable of spraying fine droplets such as a two-fluid nozzle can be used. By using such a sprayer, it is preferred to treat the surface of the filler (C) more uniformly with the coupling agent (D).

In the present embodiment, pH ₍₁₎ , pH ₍₂₎ , and (pH _{(1) -} pH ₍₂₎ ) of the sealing resin composition can be controlled, for example, by adjusting the conditions of the surface treatment. Examples of the conditions of the surface treatment include the presence or absence of a sprayer, a standing time, the presence or absence of heat treatment, and heat treatment conditions.

In addition, the coupling agent (D) is contained in the sealing resin composition by subjecting the filler (C) to the surface treatment described above, and may be contained by being directly mixed into other components in a mixer. In the resin composition for sealing.

The content of the coupling agent (D) in the resin composition for sealing is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more based on the entire resin composition for sealing. By setting the content of the coupling agent (D) to be equal to or higher than the above lower limit value, The filler (C) in the resin composition for sealing is excellent in dispersibility. Therefore, the moisture resistance reliability, the reflow resistance, and the like can be more effectively improved. On the other hand, the content of the coupling agent (D) in the resin composition for sealing is, for example, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. When the content of the coupling agent (D) is at most the above upper limit value, the fluidity of the sealing resin composition can be improved, and the moldability can be improved.

((E) ion trapping agent)

The resin composition for sealing may further contain, for example, an ion scavenger (E).

The ion scavenger (E) is not particularly limited, and examples thereof include inorganic ion exchangers such as hydrotalcites and polyvalent metal acid salts. These may be used alone or in combination of two or more. Among these, it is particularly preferable to use hydrotalcites from the viewpoint of improving high-temperature storage characteristics.

The content of the ion scavenger (E) in the resin composition for sealing is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more based on the entire resin composition for sealing. By setting the content of the ion scavenger (E) to be equal to or higher than the above lower limit value, the high-temperature storage characteristics can be more effectively improved. Moreover, corrosion between the bonding wires and the semiconductor elements can be surely suppressed, and connection reliability can be satisfactorily maintained. On the other hand, the content of the ion scavenger (E) in the resin composition for sealing is preferably, for example, 1% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.5% by mass or less. By setting the content of the ion scavenger (E) to be equal to or lower than the above upper limit value, the moisture resistance reliability or the reflow resistance of the semiconductor device can be improved.

(hardening accelerator (F))

The resin composition for sealing may contain, for example, a curing accelerator (F). The curing accelerator (F) may be one which can promote the crosslinking reaction between the epoxy group of the epoxy resin (A) and the curing agent (B) (for example, the phenolic hydroxyl group of the phenol resin-based curing agent). Sealing epoxy resin composition user.

In the present embodiment, the curing accelerator (F) may contain, for example, an organic phosphine, a tetrasubstituted fluorene compound, a phosphate betaine compound, an adduct of a phosphine compound and a hydrazine compound, an adduct of a hydrazine compound and a decane compound. a compound containing a phosphorus atom; an anthracene or a tertiary amine exemplified by 1,8-diazabicyclo(5,4,0)undecene-7, dimethylbenzylamine, 2-methylimidazole, or the like, or a hydrazine or an amine One or two or more kinds of nitrogen atom-containing compounds such as a quaternary salt. Among these, it is more preferable to contain a compound containing a phosphorus atom from the viewpoint of improving hardenability. Further, from the viewpoint of improving the balance between moldability and hardenability, it is more preferable to contain a tetra-substituted fluorene compound, a phosphate betaine compound, an addition product of a phosphine compound and a hydrazine compound, and an addition of a hydrazine compound and a decane compound. Things are latent.

Examples of the organic phosphine which can be used as the resin composition for sealing include a primary phosphine such as ethylphosphine or phenylphosphine; a secondary phosphine such as dimethylphosphine or diphenylphosphine; and trimethylphosphine and triethylphosphine. a tertiary phosphine such as tributylphosphine or triphenylphosphine.

The tetrasubstituted fluorene compound which can be used as the resin composition for sealing, for example, a compound represented by the following formula (7), and the like can be mentioned.

(In the above formula (7), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A represents that the aromatic ring has at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a sulfur. An anion of an aromatic organic acid of any functional group in the alcohol group. AH is an aromatic organic acid having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring. x, y are 1~3, z is 0~3, and x=y)

The compound represented by the formula (7) is obtained, for example, in the following manner, but is not limited thereto. First, a tetrasubstituted phosphonium halide, an aromatic organic acid, and a base are mixed in an organic solvent and uniformly mixed to produce an aromatic organic acid anion in the solution. Then, when water is added, the compound represented by the formula (7) can be precipitated. In the compound represented by the formula (7), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to a phosphorus atom are preferably a phenyl group, and AH is a compound having a hydroxyl group in the aromatic ring, that is, a phenol. And A is an anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and stilbene; and bisphenol A; , bisphenols such as bisphenol F and bisphenol S; polycyclic phenols such as phenylphenol and biphenol;

The phosphate betained compound which can be used as a resin composition for sealing is, for example, a compound represented by the following formula (8).

(In the above formula (8), R ⁸ represents an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents a hydroxyl group. f is a number of 0 to 5, and g is a number of 0 to 3)

The compound represented by the formula (8) can be obtained, for example, in the following manner. Obtained by the following steps: first, contacting a triaromatic substituted phosphine as a tertiary phosphine with a diazonium salt, The triaromatic substituted phosphine is replaced with a diazonium group having a diazonium salt. However, it is not limited to this.

The adduct of the phosphine compound and the hydrazine compound which can be used as a resin composition for sealing, for example, a compound represented by the following formula (9), and the like can be mentioned.

(In the above formula (9), P represents a phosphorus atom. R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may be the same or different from each other. ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a cyclic structure)

The phosphine compound used as an adduct of a phosphine compound and a hydrazine compound is preferably, for example, triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, or the like. The (benzyl)phosphine is equivalent to an unsubstituted aromatic ring or a substituent such as an alkyl group or an alkoxy group, and examples thereof include an alkyl group, an alkoxy group and the like which have a carbon number of 1 to 6 as a substituent. From the viewpoint of availability, triphenylphosphine is preferred.

In addition, examples of the ruthenium compound used for the addition of the phosphine compound and the ruthenium compound include benzoquinone and anthracene. Among them, p-benzoquinone is preferred in terms of storage stability.

As a method for producing an adduct of a phosphine compound and a hydrazine compound, an adduct can be obtained by contacting and mixing both an organic tertiary phosphine and a benzoquinone in a solvent which can be dissolved or the like. As a solvent, it is a ketone such as acetone or methyl ethyl ketone and has a low solubility to an adduct. Just fine. However, it is not limited to this.

In the compound represented by the formula (9), a compound in which R ¹⁰ , R ¹¹ and R ¹² bonded to a phosphorus atom are a phenyl group, and R ¹³ , R ¹⁴ and R ¹⁵ are a hydrogen atom, that is, 1, The compound obtained by adding 4-benzoquinone and triphenylphosphine is preferable in terms of the elastic modulus at the time of lowering the heat of the cured product of the sealing resin composition.

Examples of the adduct of the oxime compound and the decane compound which can be used as the resin composition for sealing include a compound represented by the following formula (10).

(In the above formula (10), P represents a phosphorus atom, and Si represents a ruthenium atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each represent an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group, and mutually R ²⁰ is an organic group bonded to the groups Y ² and Y ³ , wherein R ²¹ is an organic group bonded to the groups Y ⁴ and Y ^{5 ,} and Y ² and Y ³ represent protons. The base releases a proton-based group, and the groups Y ² and Y ^{3 in the} same molecule are bonded to the ruthenium atom to form a chelate structure. Y ⁴ and Y ⁵ represent a base on which a proton-donating group releases a proton, and the same molecule The internal groups Y ⁴ and Y ⁵ are bonded to the ruthenium atom to form a chelate structure. R ²⁰ and R ²¹ may be the same or different, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. ¹ is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group)

In the formula (10), examples of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, and a hydroxynaphthyl group. Benzyl, methyl, ethyl, n-butyl, n-octyl and cyclohexyl, etc., among these, more preferred are phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, hydroxynaphthyl, etc. An aromatic group or an unsubstituted aromatic group having a substituent such as an alkyl group, an alkoxy group or a hydroxyl group.

Further, in the formula (10), R ²⁰ is an organic group bonded to Y ² and Y ³ . Similarly, R ²¹ is an organic group bonded to the groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups in which a proton-based group releases a proton, and the groups Y ² and Y ^{3 in the} same molecule are bonded to a ruthenium atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups in which a proton-based group releases a proton, and the groups Y ⁴ and Y ^{5 in the} same molecule are bonded to a ruthenium atom to form a chelate structure. The radicals R ²⁰ and R ²¹ may be the same or different from each other, and the radicals Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. The base represented by -Y ² -R ²⁰ -Y ³ - and -Y ⁴ -R ²¹ -Y ⁵ - in the general formula (10) is a base formed by proton donor releasing two protons The proton donor is preferably an organic acid having at least two carboxyl groups or a hydroxyl group in the molecule, and more preferably an aromatic having at least two carboxyl groups or hydroxyl groups in the carbon adjacent to the aromatic ring. The compound is more preferably an aromatic compound having at least two hydroxyl groups adjacent to the carbon constituting the aromatic ring, and examples thereof include catechol, pyrogallol, 1,2-dihydroxynaphthalene, and 2,3-di. Hydroxynaphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chlorodecanoic acid, dan Nitrate, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, etc., among these, more preferably catechol, 1,2-dihydroxynaphthalene, 2,3 - Dihydroxynaphthalene.

Further, Z ¹ in the formula (10) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. An aliphatic hydrocarbon group such as an octyl group; or an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a naphthyl group or a biphenyl group; a glycidoxypropyl group, a mercaptopropyl group, an aminopropyl group or the like having a glycidyloxy group, a mercapto group or an amine group; Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable in terms of thermal stability.

The method for producing an adduct of a ruthenium compound and a decane compound is obtained by adding a decane compound such as phenyltrimethoxydecane or a proton donor such as 2,3-dihydroxynaphthalene to a flask to which methanol is added, followed by dissolution. A sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Further, a solution obtained by dissolving a tetrasubstituted phosphonium halide such as tetraphenylphosphonium bromide in methanol prepared by dissolving in advance under stirring at room temperature precipitates crystals. When the precipitated crystals are filtered, washed with water, and vacuum dried, an adduct of a ruthenium compound and a decane compound can be obtained. However, it is not limited to this.

The content of the curing accelerator (F) in the resin composition for sealing is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more based on the entire resin composition for sealing. When the content of the curing accelerator (F) is at least the above lower limit value, the deterioration of the curability of the sealing resin composition can be suppressed. On the other hand, the content of the curing accelerator (F) in the resin composition for sealing is preferably 1% by mass or less, and more preferably 0.8% by mass or less based on the entire resin composition for sealing. By setting the content of the hardening accelerator (F) to be equal to or less than the above upper limit value, it is possible to suppress a decrease in fluidity of the sealing resin composition.

In the resin composition for sealing, various additives such as carbon black, iron oxide, and the like; low-stress components such as polyoxyethylene rubber; natural wax such as carnauba wax, synthetic wax, and stearin may be appropriately blended as needed. A high-grade fatty acid such as zinc acid and a metal salt thereof or a release agent such as paraffin; a flame retardant such as aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate or phosphazene; and an antioxidant.

For the resin composition for sealing, for example, the above-mentioned respective components may be mixed by a known means, and further melt-kneaded by a kneading machine such as a roll, a kneader or an extruder, and then pulverized after cooling, etc., may be appropriately dispersed as needed. Index or liquidity, etc.

Next, the semiconductor device 100 of the present embodiment will be described.

The semiconductor device 100 includes a semiconductor element 20, a bonding wire 40, and a sealing resin 50. The bonding wire 40 is connected to the semiconductor element 20 and has Cu as a main component. Further, the sealing resin 50 is formed of a cured product of the sealing resin composition, and seals the semiconductor element 20 and the bonding wires 40.

The semiconductor element 20 is mounted on the substrate 30. The substrate 30 is, for example, a lead frame or an organic substrate. Further, the substrate 30 is connected to the bonding wire 40. FIG. 1 illustrates a case where the semiconductor element 20 is mounted on the crystal holder 32 in the substrate 30 as the lead frame via the die attach material 10. The base material 30 as the lead frame is made of, for example, a metal material mainly composed of Cu or a 42 alloy. Furthermore, the semiconductor element 20 may be disposed on other semiconductor elements.

On the upper surface of the semiconductor element 20, for example, a plurality of electrode pads 22 are formed. At least the surface layer of the electrode pad 22 provided on the semiconductor element 20 is made of, for example, a metal material mainly composed of Al. Thereby, the connection reliability of the bonding wire 40 mainly composed of Cu and the electrode pad 22 can be improved.

FIG. 1 illustrates a case where the bonding wires 40 electrically connect the electrode pads 22 of the semiconductor element 20 to the external leads 34 of the substrate 30.

The sealing resin 50 is composed of a cured product of the above-described sealing resin composition. Therefore, the semiconductor device 100 having good adhesion to the substrate 30 or the bonding wires 40, excellent reflow resistance or moisture resistance reliability, and excellent high-temperature operation characteristics can be obtained. This effect is particularly remarkable when the bonding wire 40 is composed of a metal material containing Cu as a main component and the substrate 30 is composed of a metal material containing Cu or a 42 alloy as a main component. Further, it is also possible to improve the high-temperature storage characteristics of the semiconductor device 100.

The semiconductor device 100 is manufactured, for example, in the following manner.

First, the semiconductor element 20 is mounted on the substrate 30. Then, by using Cu as a main component The bonding wires 40 interconnect the substrate 30 and the semiconductor element 20. Then, the semiconductor element 20 and the bonding wire 40 are sealed by the sealing resin composition. The method of sealing molding is not particularly limited, and examples thereof include a transfer molding method and a compression molding method. Thereby, the semiconductor device 100 can be manufactured.

Further, the present invention is not limited to the above-described embodiments, and variations, improvements, and the like within the scope of the object of the invention can be included in the present invention.

[Examples]

Next, an embodiment of the present invention will be described.

(resin composition for sealing)

Each of Examples 1 to 14 and Comparative Examples 1 and 2 was prepared in the following manner as a resin composition for sealing. First, the filler (C) was subjected to surface treatment by a blending amount of the coupling agent (D) shown in Table 1. Then, according to the composition shown in Table 1, the components were mixed at 15 to 28 ° C using a stirrer. Then, the obtained mixture was subjected to roll kneading at 70 to 100 °C. Then, the kneaded mixture was cooled and pulverized to obtain an epoxy resin composition. Furthermore, the details of the components in Table 1 are as follows. Further, the unit in Table 1 is mass%.

(A) Epoxy resin

Epoxy Resin 1: Phenol aralkyl type epoxy resin containing a stretched phenyl skeleton (NC-3000P, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy Resin 2: Biphenyl type epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation)

Epoxy resin 3: naphthalene type epoxy resin (HP-4770, manufactured by DIC Corporation)

(B) hardener

Hardener 1: phenol aralkyl resin containing a stretched phenyl skeleton (MEH-7851SS, manufactured by Mingwa Chemical Co., Ltd.)

Hardener 2: Phenol aralkyl resin containing a pendant phenyl skeleton (XLC-4L, manufactured by Mitsui Chemicals, Inc.)

Hardener 3: Trisphenol methane type phenol resin (MEH-7500, manufactured by Mingwa Chemical Co., Ltd.)

(C) filler

Filler 1: cerium oxide (average particle size 26 μm, specific surface area 2.4 mm ² /g)

Filler 2: cerium oxide (SO-25R, manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, specific surface area 6.0 mm ² /g)

(D) coupling agent

Γ-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)

(E) ion trapping agent

Hydrotalcite (DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.)

(F) hardening accelerator

Hardening accelerator 1: a compound represented by the following formula (11)

Hardening accelerator 2: a compound represented by the following formula (12)

(Synthesis method of hardening accelerator 1)

To a separable flask equipped with a cooling tube and a stirring device, 6.49 g (0.060 mol) of phenylhydrazine, 17.3 g (0.066 mol) of triphenylphosphine, and 40 ml of acetone were added, and the reaction was carried out at room temperature with stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain a dark green crystal hardening accelerator 1.

(Synthesis method of hardening accelerator 2)

2,3-dihydroxynaphthalene 12.81 g (0.080 mol), tetraphenylphosphonium bromide 16.77 g (0.040 mol) and methanol 100 ml were added to a separable flask equipped with a cooling tube and a stirring device, and stirred, etc., and the like. Dissolve evenly. When a sodium hydroxide solution obtained by dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol in advance was slowly added dropwise to the flask, crystals were precipitated. The precipitated crystals were filtered, washed with water, and vacuum dried to obtain a hardening accelerator 2.

(G) release agent

Carnauba wax

In Examples 1 to 4, 7 to 14, and Comparative Examples 1 and 2, the filler (C) was surface-treated with a coupling agent (D) as follows. First, after the filler 1 and the filler 2 are put into a stirrer, stirring is started, and the coupling agent (D) is further added thereto, and the mixture is stirred for 3.0 minutes to obtain a mixture of the filler 1, the filler 2, and the coupling agent (D). . Then, the mixture was taken out from the mixer, and the time shown in Table 1 (resting time) was allowed to stand. Thereby, the filler (C) which has been surface-treated by the coupling agent (D) is obtained.

In Example 5, after the above mixture was allowed to stand, the above was carried out at 55 ° C for 3 hours. The surface treatment was carried out in the same manner as in Example 1 except that the mixture was subjected to heat treatment.

In the same manner as in Example 1, except that the mixture of the filler 1, the filler 2 and the coupling agent (D) was obtained in the following manner, the surface treatment was carried out. First, the filler 1 and the filler 2 are put into a mixer, and the mixture is mixed. Then, the filler 1 and the filler 2 in the stirrer were sprayed with a nebulizer (D) while being stirred for 3.0 minutes to obtain a mixture of the filler 1, the filler 2, and the coupling agent (D). Then, the mixture was taken out from the mixer, and the time shown in Table 1 (resting time) was allowed to stand.

(Measurement of pH ₍₁₎ )

The pH ₍₁₎ of the obtained sealing resin composition was measured in the following Examples and Comparative Examples as follows. First, the cured product obtained by thermally curing the resin composition for sealing is pulverized at 175 ° C for 4 hours to obtain a pulverized product. The pulverization treatment was carried out by using TI-100 (manufactured by CMT Co., Ltd.) and 5.2 g of the cured product was placed in a pulverizer for 2 minutes. Then, 5 g of the above-mentioned pulverized material immediately after the pulverization was added to 50 ml of pure water. Then, the pure water was subjected to hot water extraction treatment using a pressure vessel having a container made of polytetrafluoroethylene and a metal container at 125 ° C for 20 hours. The pH of the extract thus obtained was measured by a pH meter and set to pH ₍₁₎ .

(Measurement of pH ₍₂₎ )

The pH ₍₂₎ of the obtained sealing resin composition was measured in the following Examples and Comparative Examples as follows. First, the cured product obtained by thermally curing the sealing resin composition was pulverized at 175 ° C for 4 hours to obtain a pulverized product. The pulverization treatment was carried out by using TI-100 (manufactured by CMT Co., Ltd.) and 5.2 g of the cured product was placed in a pulverizer for 2 minutes. Then, the obtained pulverized material was stored at 175 ° C for 500 hours. Then, 5 g of the above-mentioned pulverized material after storage was added to 50 ml of pure water. Then, the pure water was subjected to hot water extraction treatment using a pressure vessel having a container made of polytetrafluoroethylene and a metal container at 125 ° C for 20 hours. The pH of the extract thus obtained was measured with a pH meter and set to pH ₍₂₎ .

(Production of semiconductor device)

Each of Examples 1 to 14 and Comparative Examples 1 and 2 was fabricated into a semiconductor device in the following manner.

First, a TEG (Test Element Group) wafer (3.5 mm × 3.5 mm) equipped with an aluminum electrode pad was mounted on a crystal frame of a lead frame (lead frame material: 42 alloy) whose surface was plated with Ag. on. Then, a bonding wire made of a metal material of 99.9% of Cu was used for the electrode pad of the TEG wafer (hereinafter, the electrode pad) and the lead portion other than the lead frame, and wire bonding was performed at a line pitch of 120 μm. The structure obtained thereby was subjected to sealing molding using a resin composition for sealing at a mold temperature of 175 ° C, an injection pressure of 10.0 MPa, and a curing time of 2 minutes using a low-pressure transfer molding machine to prepare a semiconductor package (package size: 7.2 mm). ×11.5 mm × 1.95 mm). Thereafter, the obtained semiconductor was packaged and cured at 175 ° C for 4 hours to obtain a semiconductor device.

(MSL (Reflow Resistance Evaluation))

For each of Examples 1 to 14 and Comparative Examples 1 and 2, the obtained 12 semiconductor devices were allowed to stand in an environment of 85 ° C and a relative humidity of 60% for 168 hours, and then subjected to IR reflow treatment (260 ° C). Then, the inside of the semiconductor device after the treatment was observed by the ultrasonic flaw detector to calculate the area of the peeling generated at the interface between the sealing resin and the lead frame. For all the semiconductor devices, the case where the peeling area was less than 5% was referred to as ◎, the case where 5% or more and 10% or less was regarded as ○, and the case where more than 10% was exceeded as ×.

(HTSL (High Temperature Storage Characteristics Evaluation))

For each of Examples 1 to 14 and Comparative Examples 1 and 2, the obtained semiconductor device was stored in an environment of 150 ° C, and the resistance between the electrode pads of the semiconductor wafer and the bonding wires was measured every 24 hours. A semiconductor device whose value is increased by 20% from the initial value is regarded as defective. Those who did not cause a defect even if they were stored for 2,000 hours were marked as ◎, those who had a defect between 1000 and 2000 hours were recorded as ○, and those who had a defect within 1000 hours were recorded as ×.

As shown in Table 1, in Examples 1 to 14, good results were obtained regarding the reflow resistance and the high-temperature storage characteristics. Examples 1 to 6, 8, 10, and 12 to 14 showed superior high-temperature storage characteristics as compared with Examples 7, 9, and 11. Further, in Examples 2 to 14, the reflow resistance was more excellent than that of Example 1.

The application is based on the priority of Japanese Patent Application No. 2014-109860, filed on May 28, 2014, the entire disclosure of which is incorporated herein.

10‧‧‧Grain Adhesive

20‧‧‧Semiconductor components

22‧‧‧electrode pads

30‧‧‧Substrate

32‧‧‧crystal seat

34‧‧‧External leads

40‧‧‧bonding line

50‧‧‧ sealing resin

100‧‧‧Semiconductor device

Claims (5)

A resin composition for sealing, which is used for sealing a semiconductor element and a bonding wire which is connected to the semiconductor element and contains Cu as a main component; and contains an epoxy resin and a curing agent; and is determined under the following condition 1 The pH ₍₁₎ and the pH ₍₂₎ measured under the following condition 2 (pH _{(1) -} pH ₍₂₎ ) are 1.1 or less; (Condition 1: the resin composition for sealing is at 175 ° C, The hardened material obtained by thermal hardening under the condition of 4 hours was pulverized to obtain a pulverized product; then, 5 g of the pulverized material immediately after the pulverization was placed in 50 ml of pure water, and the pure water was obtained at 125 ° C for 20 hours. The hot water extraction treatment was carried out, and the pH (pH ₍₁₎ )) of the obtained extract was measured. (Condition 2: The hardened material obtained by thermally curing the resin composition for sealing at 175 ° C for 4 hours was pulverized. The pulverized material was obtained, and the pulverized material was stored at 175 ° C for 500 hours. Then, 5 g of the pulverized material after storage was placed in 50 ml of pure water, and then the pure water was subjected to 125 ° C for 20 hours. The hot water extraction treatment was carried out, and the pH (pH ₍₂₎ )) of the obtained extract was measured. The resin composition for sealing according to the first aspect of the invention is characterized in that the pH ₍₁₎ is 5 or more and 7 or less. The sealing resin composition according to claim 1 or 2, further comprising an ion scavenger. The resin composition for sealing according to the third aspect of the invention, wherein the ion is the entire solid content component of the resin composition for sealing. The content of the scavenger is 0.05% by mass or more and 1% by mass or less. A semiconductor device comprising: a semiconductor element; a bonding wire connected to the semiconductor element and containing Cu as a main component; and a sealing resin comprising the sealing resin according to any one of claims 1 to 4. The cured material is composed of a material and seals the semiconductor element and the bonding wire.