JP2017088828A - Semiconductor sealing resin composition, semiconductor device and structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor sealing resin composition that can achieve a structure which can prevent the warpage of a semiconductor device.SOLUTION: A semiconductor sealing resin composition has (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, where the (C) inorganic filler has calcium fluoride.SELECTED DRAWING: Figure 1

Description

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

  In recent years, area array packages called BGA (Ball Grid Array) and CSP (Chip Size Package) have been adopted for the purpose of high-density mounting of semiconductor chips. As this type of technology, for example, there is one described in Patent Document 1. In the semiconductor device described in this document, a semiconductor chip is mounted on a circuit board via bump connection. These circuit boards and semiconductor chips are sealed with a sealing resin layer (see FIG. 10 of Patent Document 1).

  On the other hand, in QFP (Quad Flat Package), a technique of using cristobalite as an inorganic filler in the sealing resin layer is employed for the purpose of reducing warpage between the copper lead frame and the sealing resin layer. As this type of technology, for example, there are those described in Patent Documents 2 and 3. According to this document, by using cristobalite that is slowly cooled from a high temperature, the linear expansion coefficient of the sealing resin layer at room temperature can be increased, so the difference in the linear expansion coefficient between the sealing resin layer and the copper lead frame can be reduced. It is described that it can be made smaller.

JP 2009-94250 A JP-A-11-302506 JP 2013-127710 A

  In recent semiconductor devices, there is an increasing demand for thinning. In particular, semiconductor devices having a thin sealing resin layer are increasing. In a thin semiconductor device, warping may occur when the difference in coefficient of linear expansion between constituent members of the semiconductor device such as a substrate or a sealing resin layer becomes large.

  Since the cristobalite described in Patent Documents 2 and 3 has a unique crystal structure due to its production process, the cristobalite exhibits remarkable expansion characteristics particularly during heating. Thereby, it is considered that the cristobalite can be remarkably expanded when thermosetting is performed, and the cured product (sealing resin layer) can have rigidity.

  For example, in the area array package, the linear expansion coefficient of the sealing resin layer at room temperature can be increased by employing the cristobalite described in the above document. However, as a result of studies by the present inventors, it has been found that the linear expansion coefficient of the sealing resin layer during heat tends to be lower than the target linear expansion coefficient.

  As a result of further studies, the present inventors have found that the encapsulating resin layer to which the cristobalite described in the above-mentioned document is applied has the following behavior when used in a high temperature environment. That is, it has been found that the sealing resin layer is too stiff and the coefficient of linear expansion of the sealing resin layer during heat tends to be low. As a result, a difference in thermal expansion coefficient between the sealing resin layer and the substrate is generated, and there is a possibility that the entire semiconductor device is warped.

  Based on these findings, further research on high-temperature environments has been carried out, and it has been found that by adopting calcium fluoride as an inorganic filler, the linear expansion coefficient of the sealing resin layer can be increased during heating, and the present invention has been completed. It came to do.

According to the present invention, (A) an epoxy resin,
(B) a curing agent;
(C) a semiconductor sealing resin composition comprising an inorganic filler,
There is provided a resin composition for semiconductor encapsulation, wherein the (C) inorganic filler contains calcium fluoride.

Moreover, according to the present invention, a substrate;
A semiconductor element mounted on one surface of the substrate;
A sealing resin layer for sealing the semiconductor element,
The sealing resin layer is provided with a semiconductor device composed of a cured product of the semiconductor sealing resin composition.

Moreover, according to the present invention, a substrate;
A plurality of semiconductor elements mounted on one surface of the substrate apart from each other;
A sealing resin layer that collectively seals the plurality of semiconductor elements,
The structure comprised with the hardened | cured material of the resin composition for semiconductor sealing of any one of the said sealing resin layer and Claim 1 thru | or 12 is provided.

  According to the resin composition for encapsulating a semiconductor of the present invention, it is possible to realize a structure capable of suppressing warpage of a semiconductor device.

It is sectional drawing which shows an example of the semiconductor device in this embodiment. It is sectional drawing which shows an example of the structure in this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

[Resin composition for semiconductor encapsulation]
The semiconductor sealing resin composition according to this embodiment will be described.
The resin composition for encapsulating a semiconductor according to the present embodiment includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. The (C) inorganic filler contains calcium fluoride.

  The semiconductor sealing resin composition of this embodiment is used for forming a sealing resin layer for sealing a semiconductor element (semiconductor chip) mounted on a substrate. The said sealing resin layer is comprised with the hardening body of the resin composition for semiconductor sealing.

Here, recent thin semiconductor devices are required to further reduce warpage even when used in a high temperature environment.
On the other hand, the present inventor has found that the above-described warpage can be reduced by increasing the elastic force while increasing the expansion force of the sealing resin layer when heated. Based on these findings, we have intensively studied the behavior of inorganic fillers in high-temperature environments. Among many inorganic fillers, especially by selecting calcium fluoride, the thermal expansion coefficient was increased. However, the inventors have found that the decrease in the elastic modulus during heat can be suppressed, and have completed the present invention.

  In the semiconductor sealing resin composition of the present embodiment, calcium fluoride is employed as the inorganic filler. Thereby, about the sealing resin layer which is the hardening body of the said resin composition for semiconductor sealing, the linear expansion coefficient at the time of a heat | fever can be enlarged. Moreover, about the said sealing resin layer, the elastic modulus at the time of heating can be improved. Therefore, for example, even when used in a high-temperature environment such as a vehicle, warpage of the entire semiconductor device during heat can be reduced.

  The composition of the semiconductor sealing resin composition of this embodiment will be described.

[(A) Epoxy resin]
As the (A) epoxy resin in the present embodiment, monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited. In the present embodiment, it is particularly preferable to employ a non-halogenated epoxy resin as the (A) epoxy resin.

In this embodiment, (A) epoxy resin is, for example, biphenyl type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin; stilbene type epoxy resin; phenol Novolac epoxy resins such as novolac epoxy resins and cresol novolac epoxy resins; polyfunctional epoxy resins such as triphenolmethane epoxy resins and alkyl-modified triphenolmethane epoxy resins; phenol aralkyl epoxy resins having a phenylene skeleton, biphenylene Phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a skeleton; dihydroxynaphthalene type epoxy resin, dihydroxynaphthalene A naphthol type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a monomer; a triazine core-containing epoxy resin such as triglycidyl isocyanurate or monoallyl diglycidyl isocyanurate; a bridged cyclic structure such as a dicyclopentadiene-modified phenol type epoxy resin One type or two or more types selected from hydrocarbon compound-modified phenol type epoxy resins are included.
Among these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, among bisphenol type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, phenol aralkyl type epoxy resin, and triphenolmethane type epoxy resin More preferably, at least one is included. Moreover, it is particularly preferable that at least one of a phenol aralkyl type epoxy resin and a novolac type epoxy resin is included from the viewpoint of suppressing warpage of the semiconductor device. Further, a biphenyl type epoxy resin is particularly preferable for improving fluidity, and a phenol aralkyl type epoxy resin is particularly preferable for controlling the elastic modulus at high temperature.

  Examples of the epoxy resin (A) include an epoxy resin represented by the following formula (1), an epoxy resin represented by the following formula (2), an epoxy resin represented by the following formula (3), and the following formula (4). And those containing at least one selected from the group consisting of epoxy resins represented by the following formula (5) can be used. Among these, what contains 1 or more types selected from the epoxy resin represented by following formula (1) and the epoxy resin represented by following formula (4) is mentioned as one of the more preferable aspects.

（式（１）中、Ａｒ^１はフェニレン基またはナフチレン基を表し、Ａｒ^１がナフチレン基の場合、グリシジルエーテル基はα位、β位のいずれに結合していてもよい。Ａｒ^２はフェニレン基、ビフェニレン基またはナフチレン基のうちのいずれか１つの基を表す。Ｒ_ａおよびＲ_ｂは、それぞれ独立に炭素数１〜１０の炭化水素基を表す。ｇは０〜５の整数であり、ｈは０〜８の整数である。ｎ^３は重合度を表し、その平均値は１〜３である。）

(In Formula (1), Ar ¹ represents a phenylene group or a naphthylene group, and when Ar ¹ is a naphthylene group, the glycidyl ether group may be bonded to either the α-position or the β-position. Ar ² is a phenylene group. And R _a and R _b each independently represent a hydrocarbon group having 1 to 10 carbon atoms, g is an integer of 0 to 5, and h represents _a group selected from the group consisting of a biphenylene group and a naphthylene group. Is an integer of 0 to 8. n ³ represents the degree of polymerization, and the average value is 1 to ^3. )

（式（２）中、複数存在するＲ_ｃは、それぞれ独立に水素原子または炭素数１〜４の炭化水素基を表す。ｎ^５は重合度を表し、その平均値は０〜４である。）

(In the formula (2), a plurality of R _{c s} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁵ represents a degree of polymerization, and an average value thereof is 0 to 4. )

（式（３）中、複数存在するＲ_ｄおよびＲ_ｅは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^６は重合度を表し、その平均値は０〜４である。）

(In the formula (3), a plurality of R _d and R _e each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁶ represents a degree of polymerization, and an average value thereof is 0 to 4). .)

（式（４）中、複数存在するＲ_ｆは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^７は重合度を表し、その平均値は０〜４である。）

(In the formula (4), a plurality of R _f each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁷ represents the degree of polymerization, and the average value thereof is 0 to 4. )

（式（５）中、複数存在するＲ_ｇは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^８は重合度を表し、その平均値は０〜４である。）

(In the formula (5), R _g there are a plurality, is .n ⁸ represent each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms represents the degree of polymerization, the average value is 0-4. )

The content of the epoxy resin (A) in the semiconductor sealing resin composition of the present embodiment is preferably 8% by mass or more with respect to the entire semiconductor sealing resin composition, and is 10% by mass or more. More preferably, it is particularly preferably 15% by mass or more. (A) By making content of an epoxy resin more than the said lower limit, the fluidity | liquidity of the resin composition for semiconductor sealing can be improved, and the further improvement of a moldability can be aimed at.
On the other hand, the content of the epoxy resin (A) in the resin composition for semiconductor encapsulation is preferably 50% by mass or less, and 40% by mass or less with respect to the entire resin composition for semiconductor encapsulation. It is more preferable. (A) By making content of an epoxy resin below the said upper limit, about a semiconductor device provided with the sealing resin formed using the resin composition for semiconductor sealing, moisture resistance reliability and reflow resistance are improved. be able to.

[(B) Curing agent]
The (B) curing agent in the present embodiment is not particularly limited as long as it is generally used in a resin composition for semiconductor encapsulation. For example, a phenol curing agent, an amine curing agent, and an acid anhydride type Examples thereof include a curing agent and a mercaptan curing agent. Among these, a phenolic curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like.

<Phenolic curing agent>
The phenolic curing agent is not particularly limited as long as it is generally used in a resin composition for semiconductor encapsulation. For example, phenol novolac resin, cresol novolac resin, phenol, cresol, resorcin, catechol, etc. A novolak resin obtained by condensation or cocondensation of phenols such as bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, dihydroxynaphthalene and the like with formaldehyde and ketones under an acidic catalyst, Phenol aralkyl resins having a biphenylene skeleton, phenol aralkyl resins having a phenylene skeleton and the like, synthesized from the above-mentioned phenols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl And a phenol resin having a trisphenolmethane skeleton. These may be used alone or in combination of two or more.

<Amine-based curing agent>
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone. In addition to aromatic polyamines such as (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide, and the like can be given. These may be used alone or in combination of two or more.

<Acid anhydride curing agent>
Examples of acid anhydride curing agents include alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) and maleic anhydride, trimellitic anhydride (TMA) and pyromellitic anhydride. (PMDA), aromatic acid anhydrides such as benzophenone tetracarboxylic acid (BTDA), phthalic anhydride and the like. These may be used alone or in combination of two or more.

<Mercaptan-based curing agent>
Examples of the mercaptan curing agent include trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), and the like. These may be used alone or in combination of two or more.

<Other curing agents>
Examples of other curing agents include isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins. These may be used alone or in combination of two or more.
Moreover, you may use in combination of 2 or more types of a different type | system | group hardening | curing agent among the above.

In the present embodiment, the lower limit value of the content of the (B) curing agent is preferably 0.5% by mass or more, more preferably 1% by mass or more with respect to the entire resin composition for semiconductor encapsulation. It is preferably 1.5% by mass or more. Thereby, the excellent fluidity | liquidity can be implement | achieved at the time of shaping | molding, and the improvement of a filling property or a moldability can be aimed at. On the other hand, the upper limit of the content of the curing agent (B) is preferably 9% by mass or less, more preferably 8% by mass or less, and more preferably 7% by mass with respect to the entire semiconductor sealing resin composition. % Or less is particularly preferable. Thereby, the moisture resistance reliability and reflow resistance of an electronic component can be improved. In addition, by controlling the content of the curing agent (B) in such a range, it is possible to contribute to the suppression of warpage of a molded product obtained by sealing an electronic element or the like with a semiconductor sealing resin composition. It is.
Further, when (B) the curing agent is a phenolic curing agent, the equivalent ratio of (A) the epoxy resin and (B) the curing agent, that is, the number of moles of epoxy groups in the epoxy resin / the phenolic property in the phenolic curing agent. The ratio of the number of hydroxyl groups is not particularly limited, but in order to obtain an epoxy resin composition excellent in moldability and reflow resistance, a range of 0.5 or more and 2 or less is preferable, and 0.6 or more and 1.8 or less. A range is more preferable, and a range of 0.8 to 1.5 is most preferable.

[(C) Inorganic filler]
The inorganic filler (C) of the present embodiment contains at least calcium fluoride (CaF ₂ ).

The shape of calcium fluoride that can be used in the present embodiment is not particularly limited, and either spherical or non-spherical can be used. Calcium fluoride that can be used in the present embodiment can be produced, for example, by the following process. The ore dug in the mine is washed by water and then sorted by grade. Next, it is pulverized with a pulverizer such as a ball mill, subjected to flotation with olefinic acid and sodium silicate solution, washed with water, squeezed with a filter, and dried with a dryer. Some ore has a CaF ₂ purity of about 50% before sorting, but an ore with a CaF ₂ purity of 60% or more is preferable, and an ore with 70% or more is more preferable. Further, calcium fluoride having higher purity and stable quality can be produced, for example, by a method of reacting calcium carbonate with hydrofluoric acid (hydrofluoric acid). Furthermore, spherical calcium fluoride is, for example, a powder melting method in which calcium fluoride raw material powder is passed through a high temperature region above the melting point to be spheroidized, or the calcium fluoride raw material is melted using a crucible or the like The molten metal dripped through can be produced by an atomizing method in which the molten metal is dispersed and sprayed, rapidly solidified, and spheroidized.
In the present embodiment, it is preferable to use spherical calcium fluoride from the viewpoint of enhancing the filling property into the resin composition for semiconductor encapsulation.
The calcium fluoride may be surface treated. As the surface treatment agent, for example, a coupling agent such as a silane coupling agent is used. Thereby, the fluidity | liquidity of the resin composition for semiconductor sealing can be improved.
In the spherical calcium fluoride, the roundness is preferably 0.90 or more, more preferably 0.95 or more. Thereby, the rolling resistance of the spherical calcium fluoride which is a particle in the resin composition for semiconductor sealing becomes small, and the fluidity | liquidity can be improved. Moreover, the resin composition for semiconductor sealing excellent in fluidity | liquidity can be obtained also when the filling property of calcium fluoride is improved.

The upper limit of the average particle diameter of the calcium fluoride is, for example, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. By using calcium fluoride having such a particle size, calcium fluoride can be dispersed without unevenness throughout the resin composition for semiconductor encapsulation, and as a cured resin product, heat conductivity and moisture absorption resistance can be efficiently obtained. Can be granted. On the other hand, the lower limit value of the average particle diameter of the calcium fluoride is not particularly limited, but may be 3 μm or more, for example, or 5 μm or more.
In the present specification, the “average particle size” means a 50% volume average particle size (D ₅₀ ), for example, measured using a laser diffraction scattering type particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation. can do.

The lower limit of the content of calcium fluoride is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, and 12% by mass with respect to the entire semiconductor sealing resin composition. % Or more is particularly preferable. By setting the content of calcium fluoride to the above lower limit value or more, the heat resistance and moisture absorption resistance of the semiconductor device including the sealing resin formed using the semiconductor sealing resin composition are further improved. Can do.
On the other hand, the upper limit value of the calcium fluoride content is, for example, preferably 60% by mass or less, and more preferably 50% by mass or less with respect to the entire semiconductor sealing resin composition. By making content of calcium fluoride below the said upper limit, the high fluidity | liquidity of the resin composition for semiconductor sealing can be ensured.

  Moreover, in this embodiment, (C) inorganic filler can contain other inorganic fillers other than calcium fluoride. The type of inorganic filler that can be used in combination with calcium fluoride is not particularly limited. For example, silica such as fused silica, crystalline silica, and finely divided silica, alumina, silicon nitride, aluminum nitride, aluminum hydroxide, magnesium hydroxide, and zinc borate. And zinc molybdate, and any one or more of these can be used. Among these, it is more preferable to use silica from the viewpoint of excellent versatility. Moreover, as (C) inorganic filler, you may contain the component which can provide flame retardance, such as aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.

(C) When silica is used together as the inorganic filler, for example, two or more kinds of spherical silica having different average particle diameters (D ₅₀ ) can be used in combination. This further facilitates adjustment of the linear expansion coefficients α ₁ and α ₂ of the cured product, the flexural modulus E _{(25) at 25} ° C., the flexural modulus E _{(260) at} 260 ° C., the shrinkage rate S _{1 and the} like. be able to. For this reason, it also becomes possible to contribute to suppression of the curvature of a semiconductor device.

  The silica in this embodiment can be obtained by including finely divided silica having an average particle diameter of 1 μm or less. Thereby, the filling property of the resin composition for semiconductor encapsulation can be improved. In addition, warping of the semiconductor device can be suppressed.

(C) The lower limit of the content of the entire inorganic filler is preferably 30% by mass or more, more preferably 45% by mass or more, and more preferably 50% by mass with respect to the entire semiconductor sealing resin composition. % Or more is particularly preferable. (C) By making content of an inorganic filler more than the said lower limit, the low hygroscopic property and low thermal expansion property of the sealing resin formed using the resin composition for semiconductor sealing are improved, and moisture resistance reliability And reflow resistance can be improved more effectively. On the other hand, the upper limit of the content of the (C) inorganic filler is preferably 88% by mass or less, more preferably 85% by mass or less, based on the entire semiconductor sealing resin composition. It is especially preferable to set it as 82 mass% or less. (C) By making content of an inorganic filler below the said upper limit, the moldability fall accompanying the fluid fall of the resin composition for semiconductor sealing, the bonding wire flow resulting from high viscosity, etc. It becomes possible to suppress. In addition, about the said upper limit of (C) inorganic filler, it is not restricted above, It is possible to select suitably according to physical properties, thickness, etc., such as a linear expansion coefficient of an organic substrate. From such a viewpoint, the content of the (C) inorganic filler can be 80% by mass or less or 70% by mass or less according to the type of the organic substrate.
Further, by controlling the content of the entire inorganic filler (C) within the above numerical range, the linear expansion coefficient α ₁ , α ₂ of the cured product, flexural modulus E _{(25) at 25} ° C., and 260 ° C. It becomes easier to set the physical properties such as the flexural modulus E ₍₂₆₀₎ and the shrinkage rate S ₁ in a desired range. For this reason, it also becomes possible to contribute to suppression of the curvature of a semiconductor device.

  In this embodiment, when calcium fluoride and another inorganic filler are used in combination, the lower limit of the content of calcium fluoride at the time of combined use is, for example, 5% by mass or more with respect to the entire inorganic filler (C). Is preferable, 10 mass% or more is more preferable, and 15 mass% or more is further more preferable. Thereby, the thermal elastic modulus can be improved while increasing the thermal linear expansion coefficient of the cured product of the semiconductor sealing resin composition. The upper limit of the content of calcium fluoride when used in combination is, for example, preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the entire inorganic filler (C). Thereby, for example, the effect of silica combined use can be sufficiently obtained.

[(D) Curing accelerator]
The resin composition for semiconductor encapsulation of this embodiment can further contain, for example, (D) a curing accelerator. (D) A hardening accelerator should just accelerate | stimulate the crosslinking reaction of (A) epoxy resin and (B) hardening | curing agent, and should use what is used for the resin composition for general semiconductor sealing. Can do.

  In this embodiment, (D) the curing accelerator contains phosphorus atoms such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Compound: Amidine or tertiary amine exemplified by 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole, etc. Nitrogen atom content such as quaternary salt of amidine or amine One type or two or more types selected from compounds can be included. Among these, it is more preferable that a phosphorus atom containing compound is included from a viewpoint of improving curability. In addition, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. It is more preferable to include those.

  Examples of the organic phosphine that can be used in the semiconductor sealing resin composition of the present embodiment include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, Third phosphine such as tributylphosphine and triphenylphosphine can be used.

  Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing resin composition of the present embodiment include a compound represented by the following general formula (6).

（上記一般式（６）において、Ｐはリン原子を表す。Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

(In the general formula (6), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is selected from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one functional group in the aromatic ring, AH is an aromatic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an organic acid, where x and y are numbers 1 to 3, z is a number 0 to 3, and x = y.

Although the compound represented by General formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated. In the compound represented by the general formula (6), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols. And A is preferably 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 anthraquinol, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, Examples include polycyclic phenols such as phenylphenol and biphenol.

  As a phosphobetaine compound which can be used with the resin composition for semiconductor sealing of this embodiment, the compound etc. which are represented by following General formula (7) are mentioned, for example.

（上記一般式（７）において、Ｐはリン原子を表す。Ｒ^８は炭素数１〜３のアルキル基、Ｒ^９はヒドロキシル基を表す。ｆは０〜５の数であり、ｇは０〜３の数である。）

(In the general formula (7), P represents a phosphorus atom. R ⁸ represents an alkyl group having 1 to 3 carbon atoms, R ⁹ represents a hydroxyl group. F represents a number of 0 to 5, and g represents 0 to 0. A number of 3.)

  The compound represented by the general formula (7) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the resin composition for encapsulating a semiconductor according to this embodiment include compounds represented by the following general formula (8).

（上記一般式（８）において、Ｐはリン原子を表す。Ｒ^１０、Ｒ^１１およびＲ^１２は炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ^１３、Ｒ^１４およびＲ^１５は水素原子または炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ^１４とＲ^１５が結合して環状構造となっていてもよい。）

(In the general formula (8), 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, and are the same as each other. R ¹³ , R ¹⁴ and R ¹⁵ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R ¹⁴ and R ¹⁵ are bonded to each other. And may have a circular structure.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  Moreover, as a quinone compound used for the adduct of a phosphine compound and a quinone compound, a benzoquinone and anthraquinones are mentioned, Especially, p-benzoquinone is preferable from the point of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

In the compound represented by the general formula (8), R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are phenyl groups, and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, ie, 1, A compound in which 4-benzoquinone and triphenylphosphine are added is preferable in that it reduces the thermal elastic modulus of the cured product of the encapsulating resin composition.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the semiconductor sealing resin composition of the present embodiment include compounds represented by the following general formula (9).

（上記一般式（９）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^１６、Ｒ^１７、Ｒ^１８およびＲ^１９は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^２０は、基Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^２１は、基Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^２０、およびＲ^２１は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）

(In the above general formula (9), P represents a phosphorus atom and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Represents a group, which may be the same or different from each other, wherein R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ²¹ represents the groups Y ⁴ and Y ⁵ ; Y ² and Y ³ represent a group formed by releasing a proton from a proton donating group, and groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent a group formed by releasing a proton from a proton donating group, and groups Y ⁴ and Y ⁵ in the same molecule are combined with a silicon atom to form a chelate structure. there ^{.R 20,} and ^{R 21} are mutually Or different ^{mere, Y 2, Y 3, Y} 4 and Y ⁵ may .Z ¹ also being the same or different organic group having an aromatic ring or a heterocyclic ring or fat, A group.)

In the general formula (9), 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, a hydroxynaphthyl group, a benzyl group, and a methyl group. , Ethyl group, n-butyl group, n-octyl group, cyclohexyl group and the like, among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, and alkoxy groups An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

In the general formula ^{(9), R 20} is an organic group bonded to ^{Y 2} and ^{Y 3.} Similarly, R ²¹ is an organic group that binds to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by proton-donating groups releasing protons, and groups Y ² and Y ³ in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by proton-donating groups releasing protons, and groups Y ⁴ and Y ⁵ in the same molecule are combined with a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same or different from each other, and the groups Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other. In such a group represented by —Y ² —R ²⁰ —Y ³ — and Y ⁴ —R ²¹ —Y ⁵ — in the general formula (9), the proton donor releases two protons. The proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and further has a carboxyl group or hydroxyl group on the adjacent carbon constituting the aromatic ring. An aromatic compound having at least two is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring is more preferable. For example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy Naphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy Roxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, and the like, among these, catechol, 1,2- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

Z ¹ in the general formula (9) 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, Aliphatic hydrocarbon groups such as hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group and aminopropyl group Reactive groups such as mercapto groups, alkyl groups having amino groups, and vinyl groups. Among these, methyl groups, ethyl groups, phenyl groups, naphthyl groups, and biphenyl groups are preferred from the viewpoint of thermal stability. More preferable.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

In the present embodiment, the content of the (D) curing accelerator is preferably 0.05% by mass or more, and more preferably 0.15% by mass or more with respect to the entire semiconductor sealing resin composition. More preferably, it is particularly preferably 0.25% by mass or more. (D) By making content of a hardening accelerator more than the said lower limit, sclerosis | hardenability at the time of sealing molding can be improved effectively.
On the other hand, the content of the (D) curing accelerator is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, based on the entire semiconductor sealing resin composition. . (D) The fluidity | liquidity at the time of sealing molding can be aimed at by making content of a hardening accelerator below the said upper limit.

[(E) Coupling agent]
The resin composition for semiconductor encapsulation of this embodiment can contain (E) coupling agent, for example. (E) Examples of coupling agents include epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, methacryl silane and other various silane compounds, titanium compounds, aluminum chelates, aluminum / zirconium compounds, and the like. A known coupling agent can be used. Examples of these include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, -[Bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, phenylaminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (Dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysila , Hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl) Silane coupling agents such as hydrolyzate of butylidene) propylamine, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditri) Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxya Tate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Examples thereof include titanate coupling agents such as phenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, or vinyl silane are more preferable. Further, from the viewpoint of more effectively improving the filling property and moldability, it is particularly preferable to use a secondary aminosilane represented by phenylaminopropyltrimethoxysilane.

  (E) It is preferable that content of a coupling agent is 0.1 mass% or more with respect to the whole resin composition for semiconductor sealing, and it is more preferable that it is 0.15 mass% or more. (E) By making content of a coupling agent more than the said lower limit, the dispersibility of (C) inorganic filler can be made favorable. On the other hand, the content of the (E) coupling agent is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the entire semiconductor sealing resin composition. (E) By making content of a coupling agent below the said upper limit, the fluidity | liquidity of the resin composition at the time of sealing molding can be improved, and a fillability and a moldability can be aimed at.

[(F) Other ingredients]
The resin composition for encapsulating a semiconductor according to the present embodiment further includes an ion scavenger (ion catcher) such as hydrotalcite; a colorant such as carbon black or bengara; a natural wax such as carnauba wax; Synthetic waxes such as acid ester waxes, higher fatty acids such as zinc stearate and metal salts thereof or mold release agents such as paraffin; various additives such as antioxidants may be appropriately blended.

  Moreover, the resin composition for sealing of this embodiment can contain a low stress agent, for example. Examples of the low stress agent include silicone oil, silicone rubber, polyisoprene, 1,2-polybutadiene, 1,4-polybutadiene and other polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene, poly (oxypropylene), poly One or more selected from thermoplastic elastomers such as (oxytetramethylene) glycol, polyolefin glycol, poly-ε-caprolactone, polysulfide rubber, and fluororubber can be included. Among these, the inclusion of at least one of silicone rubber, silicone oil, and acrylonitrile-butadiene rubber controls the bending elastic modulus and shrinkage to a desired range and suppresses the occurrence of warpage of the resulting semiconductor package. From the viewpoint, it can be selected as a particularly preferred embodiment.

  When this low-stress agent is used, the content of the entire low-stress agent is preferably 0.05% by mass or more and 0.10% by mass or more with respect to the entire resin composition for semiconductor encapsulation. Is more preferable. On the other hand, the content of the low stress agent is preferably 1% by mass or less, and more preferably 0.5% by mass or less, based on the entire semiconductor sealing resin composition. By controlling the content of the low stress agent in such a range, warpage of the obtained semiconductor package can be more reliably suppressed.

  The manufacturing method of the resin composition for semiconductor sealing of this embodiment is demonstrated. For example, first, each raw material component described above is mixed by a known means to obtain a mixture. Furthermore, a kneaded product is obtained by melt-kneading the mixture. As the kneading method, for example, an extrusion kneader such as a single-screw kneading extruder, a biaxial kneading extruder, or a roll kneader such as a mixing roll can be used, but a twin-screw kneading extruder is used. It is preferable. After cooling, the kneaded product can be granulated, granulated, or tableted.

  Examples of a method for obtaining a powdery resin composition include a method of pulverizing a kneaded product using a pulverizer. You may grind | pulverize what kneaded material shape | molded into the sheet | seat. As the pulverizer, for example, a hammer mill, a stone mill type grinder, a roll crusher, or the like can be used.

  As a method for obtaining a granular or powdery resin composition, for example, a die having a small diameter is installed at the outlet of a kneading apparatus, and a kneaded material in a molten state discharged from the die is fixed to a predetermined length with a cutter or the like. A granulation method typified by a hot-cut method of cutting into two can also be used. In this case, after obtaining a granular or powdery resin composition by a granulation method such as a hot cut method, it is preferable to perform deaeration before the temperature of the resin composition is lowered so much.

  When manufacturing a tablet-shaped molded object, the method of tablet-molding or compression-molding a powdery resin composition with a molded object manufacturing apparatus (tablet apparatus) is mentioned. Moreover, as a resin composition for semiconductor sealing of this embodiment, what adjusted the dispersity, fluidity | liquidity, etc. suitably can be used as needed.

  The characteristic of the resin composition for semiconductor encapsulation of this embodiment is demonstrated.

The resin composition for semiconductor encapsulation of the present embodiment 175 ° C., after heat treatment at 3 min, 175 ° C., the cured product obtained by heat treatment at 4 hours, the lower limit of the linear expansion coefficient alpha ₂ of the glass transition temperature or higher For example, the value is preferably 30 ppm / K or more, more preferably 35 ppm / K or more, further preferably 40 ppm / K or more, and particularly preferably 42 ppm / K or more. Thereby, it is possible to approach the linear expansion coefficient of the substrate during heating. On the other hand, the upper limit of the linear expansion coefficient alpha ₂ of the cured product, for example, may be less 200 ppm / K, preferably not more than 100ppm / K, 80ppm / K or less, and even more preferably less 60 ppm / K . Dissociation from the linear expansion coefficient of the substrate during heating can be suppressed.

As described above, in recent years, there has been an increasing demand for suppressing the occurrence of warpage, particularly for thin semiconductor devices. In addition, from the viewpoint of expanding the application range of semiconductor devices, there is a high demand for suppressing warpage during heat.
As a result of intensive studies by the present inventors in response to such a demand, a semiconductor element is mounted by adjusting the linear expansion coefficient α ₂ to the specific range for the cured resin composition for semiconductor encapsulation. It was found that the difference in thermal expansion coefficient with the substrate to be reduced can be alleviated and the warpage of the entire semiconductor device is suppressed.

The lower limit of the flexural modulus E ₍₂₆₀₎ at 260 ° C. of the cured product obtained by heat-treating the resin composition for semiconductor encapsulation of this embodiment at 175 ° C. for 3 minutes and then 175 ° C. for 4 hours. For example, the value is preferably 1000 MPa or more, more preferably 1100 MPa or more, and further preferably 1200 MPa or more. By setting the flexural modulus E ₍₂₆₀₎ at 260 ° C. to be equal to or higher than the above lower limit value, it is possible to stably control the warp of the semiconductor device.
On the other hand, the upper limit value of the flexural modulus E ₍₂₆₀₎ at 260 ° C. is not particularly limited, but may be, for example, 2000 MPa or less, preferably 1900 MPa or less, and more preferably 1800 MPa or less. By setting the flexural modulus E ₍₂₆₀₎ at 260 ° C. to the upper limit value or less, it is possible to impart moderate flexibility as a sealing resin, effectively relieving external stress and thermal stress. In addition, it is possible to improve solder resistance reliability during reflow.

In the cured product using the semiconductor sealing resin composition of the present embodiment, the linear expansion coefficient α ₂ and the flexural modulus E _{(260) at} 260 ° C. can be satisfied simultaneously. Thereby, it is possible to well reduce the warpage of the entire semiconductor device in a high temperature environment.

The linear expansion coefficient α ₁ below the glass transition temperature of a cured product obtained by heat-treating the resin composition for semiconductor encapsulation of this embodiment at, for example, 175 ° C. for 3 minutes and then heat-treating at 175 ° C. for 4 hours. The lower limit of is, for example, preferably 5 ppm / K or more, more preferably 10 ppm / K or more, and further preferably 15 ppm / K or more. On the other hand, the upper limit of the linear expansion coefficient alpha ₁ in below the glass transition temperature, for example, is preferably from 40 ppm / K or less, and more preferably 35 ppm / K or less, and more preferably 30 ppm / K. By setting the linear expansion coefficient α ₁ within the above numerical range, it is possible to suppress the occurrence of warpage in the semiconductor package due to the difference in the linear expansion coefficient between the substrate and the sealing resin even under relatively low temperature conditions. It becomes.

The cured resin obtained by heat-treating the resin composition for encapsulating a semiconductor of this embodiment at, for example, 175 ° C. for 3 minutes and then heat-treating at 175 ° C. for 4 hours has a flexural modulus E ₍₂₅₎ at 25 ° C. For example, the lower limit is preferably 1.0 GPa or more, more preferably 3.0 GPa or more, and further preferably 5.0 GPa or more. By setting the flexural modulus E ₍₂₅₎ at 25 ° C. to be equal to or higher than the lower limit, it is possible to more effectively suppress the warp of the semiconductor device at room temperature.
On the other hand, the upper limit value of the flexural modulus E ₍₂₅₎ at 25 ° C. of the cured product is not particularly limited, but is preferably 40 GPa or less, preferably 30 GPa or less, and more preferably 20 GPa or less. By setting the bending elastic modulus E ₍₂₅₎ at 25 ° C. of the cured product to be equal to or less than the above upper limit value, it is possible to effectively relieve external stress and improve the reliability of the semiconductor device.

  The lower limit value of the glass transition temperature of the cured product obtained by heat-treating the resin composition for semiconductor encapsulation of this embodiment at 175 ° C. for 3 minutes and then heat-treating at 175 ° C. for 4 hours is, for example, 130 ° C or higher is preferable, 140 ° C or higher is more preferable, and 150 ° C or higher is more preferable. By setting the glass transition temperature to the above temperature or more, the semiconductor element can be stably sealed even when heated. On the other hand, the upper limit value of the glass transition temperature of the cured product is not particularly limited, but may be, for example, 250 ° C. or lower, or 230 ° C. or lower.

The linear expansion coefficients α ₁ and α ₂ and the glass transition temperature of a cured product obtained by curing the semiconductor sealing resin composition of the present embodiment are, for example, using a thermomechanical analyzer (manufactured by Seiko Electronics Co., Ltd., TMA100). The measurement can be performed under the conditions of a measurement temperature range of 0 ° C. to 320 ° C. and a heating rate of 5 ° C./min. Measurement of the flexural modulus at 260 ° C. and 25 ° C. can be performed in accordance with JIS K 6911.

Further, the resin composition for semiconductor encapsulation of the present embodiment, 175 ° C., the lower limit of the shrinkage factor S ₁ when heat treated at 3 minutes, for example, preferably not less than 0.3%, more than 0.4% More preferred is 0.5% or more. On the other hand, the upper limit of the shrinkage factor _{S 1,} for example, preferably 2.0% or less, more preferably 1.5% or less. Thus, by making the shrinkage rate at the time of molding of the resin composition for semiconductor encapsulation into a specific range, the shrinkage amount of the substrate such as an organic substrate and the shrinkage amount at the time of curing of the resin composition can be matched, and the semiconductor. The package can be stabilized in a shape in which warpage is suppressed.

The shrinkage factor S ₁ can be measured, for example, as follows. First, using a transfer molding machine, a resin composition for semiconductor encapsulation is injected and molded into a mold cavity under a mold temperature of 175 ° C., a molding pressure of 9.8 MPa, and a curing time of 3 minutes. Make a piece. Subsequently, the said test piece is cooled to 25 degreeC. Here, the shrinkage rate S ₁ (%) is calculated from the inner diameter dimension of the mold cavity at 175 ° C. and the outer dimension dimension of the test piece at 25 ° C. as follows.
S ₁ = {(inner diameter of mold cavity at 175 ° C.) − (Outer diameter of test piece at 25 ° C.)} / (Inner diameter of mold cavity at 175 ° C.) × 100

The semiconductor device of this embodiment will be described.
The semiconductor device of this embodiment includes a substrate, a semiconductor element, and a sealing resin layer.
In the present embodiment, for example, an organic substrate such as an interposer can be used as the substrate. The semiconductor element (semiconductor chip) is mounted on one surface of the substrate. The semiconductor element is electrically connected to the substrate by, for example, wire bonding or flip chip connection. A plurality of semiconductor elements may be mounted. For example, the plurality of semiconductor elements may be arranged on the mounting surface of the substrate so as to be separated from each other, but may be arranged in a stacked manner. Different types of semiconductor elements may be used.

  The semiconductor sealing resin composition of this embodiment is used for forming a sealing resin layer for sealing a semiconductor element mounted on a substrate. The sealing molding using the resin composition for semiconductor encapsulation is not particularly limited, and examples thereof include a transfer molding method and a compression molding method.

  The semiconductor device of the present embodiment is not particularly limited. For example, QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip Size Package), and QFN (Quad Flat Non). Package), SON (Small Outline Non-leaded Package), LF-BGA (Lead Frame BGA). For BGA and CSP, an overmold type in which the upper surface of the semiconductor element (the top surface opposite to the mounting surface) is covered with a sealing resin layer may be used, and the upper surface of the semiconductor element is exposed from the sealing resin. It may be an exposed type package.

  The resin composition for encapsulating a semiconductor according to the present embodiment can also be used for a structure formed by MAP (Mold Array Package) molding that is often applied to the molding of the package. The said structure is obtained by sealing the several semiconductor element mounted on a board | substrate collectively using the resin composition for semiconductor sealing of this embodiment.

  The effect of suppressing the warpage of the semiconductor device in the present embodiment is that, among BGAs and CSPs, BGAs and CSPs of a type in which the thickness of the sealing resin is thinner than the thickness of the substrate, and the upper surface of the semiconductor element are exposed from the sealing resin. This is particularly noticeable in a package such as an exposed type BGA or CSP in which the sealing resin is not sufficiently effective to suppress deformation due to expansion and contraction of the substrate.

  The resin composition for semiconductor encapsulation of this embodiment can be used as a mold underfill material, for example. The mold underfill material is a material that collectively performs the sealing of the semiconductor element disposed on the substrate and the filling of the gap between the substrate and the semiconductor element. Thereby, the man-hour in the manufacture of the semiconductor device can be reduced. In addition, since the semiconductor sealing resin composition according to this embodiment can be filled between the substrate and the semiconductor element, it is also possible to more effectively suppress the warpage of the semiconductor device.

  In the semiconductor sealing resin composition of the present embodiment, the flow length of the spiral flow is preferably 110 cm or more, more preferably 120 cm or more, and particularly preferably 130 cm or more. Thereby, the filling property at the time of filling the resin composition for semiconductor sealing between a board | substrate and a semiconductor element can be improved more effectively. The upper limit value of the flow length of the spiral flow is not particularly limited, but can be, for example, 200 cm. The spiral flow is measured using, for example, a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) and a mold for spiral flow measurement in accordance with EMMI-1-66 at a mold temperature of 175 ° C. The sealing resin composition is injected under conditions of an injection pressure of 9.8 MPa and a curing time of 3 minutes, and the flow length is measured. In the present embodiment, for example, the spiral flow can be increased by using fused spherical silica as a filler, lowering the softening point of an epoxy resin or a curing agent, or reducing the amount of a curing accelerator.

  In the present embodiment, a semiconductor package in which a semiconductor element is mounted on one surface of an organic substrate can be cited as an example of a semiconductor device formed using a semiconductor sealing resin composition. In this case, the one surface of the organic substrate and the semiconductor element are sealed with the semiconductor sealing resin composition. That is, a single-side sealed package is obtained. In addition, a plurality of solder balls are formed as external connection terminals, for example, on the other surface opposite to the one surface of the organic substrate. In such a semiconductor package, the upper surface of the semiconductor element may be sealed with a sealing resin, or may be exposed from the sealing resin.

  In such a semiconductor package, for example, the thickness of the sealing resin may be 0.4 mm or less, or 0.3 mm or less. Thereby, the semiconductor package can be thinned. Moreover, even in such a thin semiconductor package, the occurrence of package warpage can be suppressed by using the semiconductor sealing resin composition according to the present embodiment. Here, the thickness of the sealing resin refers to the thickness of the sealing resin based on the one surface in the normal direction of the one surface of the organic substrate. Moreover, in this embodiment, the thickness of sealing resin can be made below into the thickness of an organic substrate, for example. Thereby, the semiconductor package can be thinned more efficiently.

  The resin composition for semiconductor encapsulation of this embodiment is, for example, in the form of powder, granules or tablets. This makes it possible to perform sealing molding using a transfer molding method, a compression molding method, or the like. In this embodiment, a granular material refers to either a powder form or a granular form. Moreover, the resin composition for semiconductor sealing of a tablet is good also as a B-stage state.

Next, the semiconductor device 100 will be described with reference to FIG.
FIG. 1 is a cross-sectional view illustrating an example of the semiconductor device 100.

  The semiconductor device 100 includes a substrate 10, a semiconductor element 20 mounted on one surface of the substrate 10, and a sealing resin layer 30 that seals the one surface of the substrate 10 and the semiconductor element 20. It is a package. That is, the semiconductor device 100 is a single-side sealed semiconductor package in which the other surface of the substrate 10 opposite to the one surface is not sealed with the sealing resin layer 30. The sealing resin layer 30 is comprised by the hardened | cured material of the resin composition for semiconductor sealing of this embodiment. Thereby, since the linear expansion coefficient of the sealing resin layer 30 during heat can be increased, the difference in thermal expansion coefficient between the sealing resin layer 30 and the substrate 10 can be decreased. Therefore, the entire warp of the semiconductor device 100 can be suppressed when used in a high temperature environment.

  In the present embodiment, the upper surface of the semiconductor element 20 may be covered with the sealing resin layer 30 (FIG. 1), or may be exposed from the sealing resin layer 30 (not shown).

  In the example shown in FIG. 1, the substrate 10 is an organic substrate. For example, a plurality of solder balls 12 are provided on the back surface of the substrate 10 opposite to the front surface (mounting surface) on which the semiconductor element 20 is mounted. Further, the semiconductor element 20 is flip-chip mounted on the substrate 10, for example. The semiconductor element 20 is electrically connected to the substrate 10 through a plurality of bumps 22, for example. As a modification, the semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire.

  In the example shown in FIG. 1, the gap between the semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. The underfill 32 and the sealing resin layer 30 may be made of different materials, but may be made of the same material. The resin composition for semiconductor encapsulation of this embodiment can be used as a mold underfill material. For this reason, the underfill 32 and the sealing resin layer 30 can be formed of the same material and can be formed in the same process. Specifically, a sealing step of sealing the semiconductor element 20 with a semiconductor sealing resin composition, and a filling step of filling the gap between the substrate 10 and the semiconductor element 20 with the semiconductor sealing resin composition; Can be carried out in the same process (collectively).

In this embodiment, the thickness of the sealing resin layer 30 is, for example, from the mounting surface of the substrate 10 (one surface opposite to the surface on which the external connection-like bumps 12 are formed) to the top of the sealing resin layer 30. It may be the shortest distance to the surface. The thickness of the sealing resin layer 30 refers to the thickness of the sealing resin layer 30 based on the one surface in the normal direction of one surface of the substrate 10 on which the semiconductor element 20 is mounted. In this case, the upper limit value of the thickness of the sealing resin layer 30 may be 0.4 mm or less, 0.3 mm or less, or 0.2 mm or less, for example. On the other hand, the lower limit value of the thickness of the sealing resin layer 30 is not particularly limited, but may be, for example, 0 mm or more (exposed type) or 0.01 mm or more.
Further, the upper limit value of the thickness of the substrate 10 may be, for example, 0.8 mm or less, or 0.4 mm or less. On the other hand, the lower limit value of the thickness of the substrate 10 is not particularly limited, but may be, for example, 0.1 mm or more.
According to this embodiment, the semiconductor package can be thinned in this way. Moreover, even if it is a thin semiconductor package, it becomes possible to suppress the curvature of the semiconductor device 100 by forming the sealing resin layer 30 using the semiconductor sealing resin composition according to the present embodiment. . In the present embodiment, for example, the thickness of the sealing resin layer 30 can be set to be equal to or less than the thickness of the substrate 10. Thereby, the semiconductor device 100 can be thinned more efficiently.

Next, the structure 102 will be described.
FIG. 2 is a cross-sectional view illustrating an example of the structure body 102. The structure 102 is a molded product formed by MAP molding. For this reason, a plurality of semiconductor packages are obtained by dividing the structure 102 into pieces for each semiconductor element 20.

  The structure 102 includes a substrate 10, a plurality of semiconductor elements 20, and a sealing resin layer 30. The plurality of semiconductor elements 20 are arranged on one surface of the substrate 10. FIG. 2 illustrates a case where each semiconductor element 20 is flip-chip mounted on the substrate 10. In this case, each semiconductor element 20 is electrically connected to the substrate 10 via a plurality of bumps 22. On the other hand, each semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire. Note that the substrate 10 and the semiconductor element 20 can be the same as those exemplified in the semiconductor device 100.

  In the example shown in FIG. 2, the gap between each semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. On the other hand, the above-mentioned resin composition for encapsulating a semiconductor can also be used as a mold underfill material. In this case, the sealing of the semiconductor element 20 and the filling of the gap between the substrate 10 and the semiconductor element 20 are performed collectively.

  The sealing resin layer 30 seals the plurality of semiconductor elements 20 and the one surface of the substrate 10. In this case, the other surface of the substrate 10 opposite to the one surface is not sealed with the sealing resin layer 30. Moreover, the sealing resin layer 30 is comprised by the hardened | cured material of the resin composition for semiconductor sealing mentioned above. Accordingly, warping of the structure body 102 and a semiconductor package obtained by dividing the structure body 102 into pieces can be suppressed. The sealing resin layer 30 is formed, for example, by sealing and molding a semiconductor sealing resin composition using a known method such as a transfer molding method or a compression molding method. In the present embodiment, the upper surface of each semiconductor element 20 may be sealed with the sealing resin layer 30 as shown in FIG. 2 or may be exposed from the sealing resin layer 30.

  As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to the said embodiment, The structure can also be changed in the range which does not change the summary of this invention.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all.

It shows below about the component used by each Example and each comparative example.
(Preparation of resin composition for sealing)
First, after mixing each raw material mix | blended according to Table 1 using the mixer at normal temperature, it roll-kneaded at 70-100 degreeC. Subsequently, after cooling the obtained kneaded material, this was grind | pulverized and the resin composition for sealing was obtained. Details of each component in Table 1 are as follows. Moreover, the unit in Table 1 is mass%.

(A) Epoxy resin Epoxy resin 1: Cresol novolac type epoxy resin (manufactured by DIC Corporation, N-660)

(B) Curing agent Curing agent 1: Phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3)

(C) Inorganic filler Inorganic filler 1: Spherical calcium fluoride (manufactured by Denka Co., Ltd., CAF, average particle diameter (D ₅₀ ) 10 μm, roundness 0.93)
Inorganic filler 2: Spherical fused silica (manufactured by Denka Co., Ltd., trade name “FB560”, average particle size (D ₅₀ ) 30 μm).
Inorganic filler 3: spherical fused silica (fine powder) (manufactured by Admatechs Co., Ltd., SO-C2, average particle diameter (D ₅₀ ) 0.5 μm)
Inorganic filler 4: Spherical fused silica (manufactured by Admatechs, SO-C5, average particle size (D ₅₀ ) 1.6 μm)
Inorganic filler 5: Aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., CL-303, average particle size (D ₅₀ ) 5.2 μm)
As a method for producing the spherical calcium fluoride as the inorganic filler 1, a calcium fluoride raw material powder having an average particle diameter (D ₅₀ ) of 10 μm was passed through a high temperature region of 1600 ° C. which is equal to or higher than the melting point to be spheroidized. . The purity of the calcium fluoride raw material powder used is 90%.
[Roundness]
Roundness was calculated using the following general formula (1). In the formula, α represents the actual area of the projected image of the object (spherical calcium fluoride) 10 g that is the object of roundness calculation. α ′ indicates the area of a perfect circle having a perimeter of PM when the perimeter of the projection image (= PM). Therefore, when the roundness is 1, the object is a perfect circle. If the object has irregularities, the roundness decreases. For measuring the roundness, FPIP-2100 manufactured by Sysmex Corporation was used.
Roundness = α / α ′ = α × 4π / (PM) ² (1)
In addition, the average particle diameter in a present Example was measured using Shimadzu Corporation laser diffraction scattering type particle size distribution analyzer SALD-7000.

(D) Curing accelerator Curing accelerator 1: Tetra-substituted phosphonium compound represented by the following formula (13) synthesized by the following method

[Synthesis Method of Tetra-Substituted Phosphonium Compound Represented by Formula (13) above]
In a separable flask equipped with a condenser and a stirrer, 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol were charged and stirred to dissolve uniformly. It was. When a sodium hydroxide solution prepared by previously dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a tetra-substituted phosphonium compound represented by the above formula (13).

(E) Coupling agent Coupling agent: Phenylaminopropyltrimethoxysilane (manufactured by Dow Corning Toray, CF4083)

(F) Other separable agents: montanic acid ester wax (WE-4 (manufactured by Clariant Japan Co., Ltd.))
Ion catcher: Hydrotalcite (DHT-4H (manufactured by Kyowa Chemical Industry Co., Ltd.))
Colorant: Carbon black (Carbon # 5 (Mitsubishi Chemical Corporation))
Low-stress agent 1: Acrylonitrile-butadiene rubber (manufactured by Ube Industries, CTBN1008SP)

[Evaluation item]
(Shrinkage factor)
About each of each Example and each comparative example, the shrinkage rate of the obtained resin composition for sealing was measured as follows. First, using a transfer molding machine, a sealing resin composition is injected and molded into a mold cavity under conditions of a mold temperature of 175 ° C., a molding pressure of 9.8 MPa, and a curing time of 3 minutes. Was made. The specimen was then cooled to 25 ° C. Here, the shrinkage rate S ₁ (%) was calculated from the inner diameter dimension of the mold cavity at 175 ° C. and the outer dimension dimension of the test piece at 25 ° C. as follows.
S ₁ = {(inner diameter of mold cavity at 175 ° C.) − (Outer diameter of test piece at 25 ° C.)} / (Inner diameter of mold cavity at 175 ° C.) × 100
The results are shown in Table 1.

(Glass transition temperature, linear expansion coefficient (α ₁ , α ₂ ))
About each Example and each comparative example, the glass transition temperature and the linear expansion coefficient of the hardened | cured material of the obtained sealing resin composition were measured as follows. First, a sealing resin composition was injection molded using a transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 3 minutes to obtain a 15 mm × 4 mm × 4 mm test piece. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, using a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100), a measurement temperature range of 0 ° C. to 320 ° C., a rate of temperature increase The measurement was performed under the condition of 5 ° C./min. From this measurement result, the linear expansion coefficient (α ₁ ) below the glass transition temperature and the linear expansion coefficient (α ₂ ) above the glass transition temperature were calculated. In Table 1, the unit of α ₁ and α ₂ is ppm / K, and the unit of glass transition temperature is ° C. The results are shown in Table 1.

(Bending elastic modulus, bending strength)
About each Example and each comparative example, the bending elastic modulus and bending strength of the hardened | cured material of the obtained resin composition for sealing were measured as follows. First, using a transfer molding machine, a sealing resin composition was injection molded at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 3 minutes, and a test piece having a width of 10 mm × a thickness of 4 mm × a length of 80 mm was obtained. Obtained. Subsequently, the obtained test piece was post-cured at 175 ° C. for 4 hours. Next, the flexural modulus E ₍₂₅₎ at ₂₅ ° C. and the flexural modulus E _{(260) at} 260 ° C. of the test piece were measured according to JIS K 6911. The unit of flexural modulus is MPa. The results are shown in Table 1.

(Evaluation of warpage suppression)
About each Example and each comparative example, evaluation of curvature suppression was performed as follows. First, the following type of package (hereinafter abbreviated as PKG) was prepared using a transfer molding machine for MAP molding. A PKG designed to have a PKG size of 14 × 14 × 0.48 mm, a substrate thickness of 0.28 mm, and a resin thickness of 0.20 mm was used on a substrate mounted with a 10 × 10 × 0.15 mm Si chip. . Next, the warpage of PKG was measured. The measurement of the warpage was carried out by measuring the PKG warpage at 25 ° C. and 260 ° C. by using a shadow moire (manufactured by Akrometrix), raising the temperature from 25 ° C. to 260 ° C. Then, for both conditions of 25 ° C. and 260 ° C., warpage suppression evaluation was performed with a case where the PKG warp was less than 100 μm as ◯ and a case where the PKG warp was 100 μm or more as x. The results are shown in Table 1.

As shown in Table 1, the resin composition for semiconductor encapsulation of each embodiment, a relatively high value of coefficient of linear expansion alpha ₂ when cured. Therefore, even when the semiconductor package is manufactured, the warp can be suppressed.

DESCRIPTION OF SYMBOLS 100 Semiconductor device 102 Structure 10 Board | substrate 12 Solder ball 20 Semiconductor element 22 Bump 30 Sealing resin layer 32 Underfill

Claims (16)

(A) an epoxy resin;
(B) a curing agent;
(C) a semiconductor sealing resin composition comprising an inorganic filler,
(C) The resin composition for semiconductor sealing in which the inorganic filler contains calcium fluoride. The resin composition for semiconductor encapsulation according to claim 1,
A resin composition for encapsulating a semiconductor, wherein the calcium fluoride contains spherical calcium fluoride having a roundness of 0.9 or more. The resin composition for semiconductor encapsulation according to claim 1 or 2,
Linear expansion coefficient alpha ₂ at or above the glass transition temperature of the cured product obtained by using the semiconductor encapsulating resin composition is not more than 30 ppm / K or more 200 ppm / K,
The resin composition for semiconductor sealing whose bending elastic modulus E _{(260) in 260} degreeC of the said hardened | cured material is 1000 Mpa or more. It is the resin composition for semiconductor sealing of any one of Claim 1 to 3,
The resin composition for semiconductor sealing whose glass transition temperature of the hardened | cured material formed using the said resin composition for semiconductor sealing is 130 degreeC or more and 250 degrees C or less. The resin composition for semiconductor encapsulation according to any one of claims 1 to 4,
The resin composition for semiconductor sealing whose content of the said (C) inorganic filler is 30 to 85 mass% with respect to the said whole resin composition for semiconductor sealing. A resin composition for encapsulating a semiconductor according to any one of claims 1 to 5,
The resin composition for semiconductor sealing whose bending elastic modulus E _{(260) in 260} degreeC of the hardened | cured material formed using the said resin composition for semiconductor sealing is 2000 Mpa or less. It is the resin composition for semiconductor sealing of any one of Claim 1 thru | or 6, Comprising:
The resin composition for semiconductor sealing whose average particle diameter of the said calcium fluoride is 20 micrometers or less. A resin composition for semiconductor encapsulation according to any one of claims 1 to 7,
The said (C) inorganic filler is a resin composition for semiconductor sealing further containing a silica. The resin composition for semiconductor encapsulation according to claim 8,
The said silica is a resin composition for semiconductor sealing containing 2 or more types of spherical silica from which average particle diameter differs. The resin composition for semiconductor encapsulation according to claim 8 or 9,
The said silica is a resin composition for semiconductor sealing containing the fine powder silica with an average particle diameter of 1 micrometer or less. The resin composition for semiconductor encapsulation according to any one of claims 1 to 10,
The semiconductor sealing resin composition further includes (D) a curing accelerator,
The resin composition for semiconductor sealing in which the said (D) hardening accelerator contains 1 or more types chosen from the compound shown by following General formula (6)-(9).

(In the general formula (6), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is selected from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one functional group in the aromatic ring, AH is an aromatic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an organic acid, where x and y are numbers 1 to 3, z is a number 0 to 3, and x = y.

(In the general formula (7), P represents a phosphorus atom. R ⁸ represents an alkyl group having 1 to 3 carbon atoms, R ⁹ represents a hydroxyl group. F represents a number of 0 to 5, and g represents 0 to 0. A number of 3.)

(In the general formula (8), 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, and are the same as each other. R ¹³ , R ¹⁴ and R ¹⁵ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R ¹⁴ and R ¹⁵ are bonded to each other. And may have a circular structure.)

(In the above general formula (9), P represents a phosphorus atom and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Represents a group, which may be the same or different from each other, wherein R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ²¹ represents the groups Y ⁴ and Y ⁵ ; Y ² and Y ³ represent a group formed by releasing a proton from a proton donating group, and groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent a group formed by releasing a proton from a proton donating group, and groups Y ⁴ and Y ⁵ in the same molecule are combined with a silicon atom to form a chelate structure. there ^{.R 20,} and ^{R 21} are mutually Or different ^{mere, Y 2, Y 3, Y} 4 and Y ⁵ may .Z ¹ also being the same or different organic group having an aromatic ring or a heterocyclic ring or fat, A group.) A resin composition for semiconductor encapsulation according to any one of claims 1 to 11,
A semiconductor sealing resin composition used as a mold underfill material. A resin composition for semiconductor encapsulation according to any one of claims 1 to 12,
A resin composition for encapsulating a semiconductor which is in the form of powder, granules or tablets. A substrate,
A semiconductor element mounted on one surface of the substrate;
A sealing resin layer for sealing the semiconductor element,
The said sealing resin layer is a semiconductor device comprised by the hardened | cured material of the resin composition for semiconductor sealing of any one of Claim 1 thru | or 13. The semiconductor device according to claim 14.
The thickness of the sealing resin layer from the one surface of the substrate to the top surface of the sealing resin layer is 0.4 mm or less. A substrate,
A plurality of semiconductor elements mounted on one surface of the substrate apart from each other;
A sealing resin layer that collectively seals the plurality of semiconductor elements,
The structure comprised by the hardened | cured material of the resin composition for semiconductor sealing of any one of the said sealing resin layer and Claim 1 thru | or 13.

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