JP4618407B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device - Google Patents

Description

The present invention is an insulating material, laminates, composites, adhesives, flowable containing surface-treated inorganic filler may be used such as paint, an epoxy resin composition for semiconductor encapsulation having excellent formability, and the epoxy resin The present invention relates to a highly reliable semiconductor device bonded and / or sealed with a composition.

  Conventionally, electronic parts such as diodes, transistors, and integrated circuits are mainly sealed with an epoxy resin composition. These epoxy resin compositions are required to have good flowability in low-pressure transfer molding, filling properties, moldability such as curability for improving productivity, and semiconductor devices obtained by using them are used in semiconductor devices. High thermal shock resistance is required. In order to improve the moldability, especially the filling property of the epoxy resin composition, a low melt viscosity resin is used to maintain high fluidity at low viscosity at the time of molding, and to improve the thermal shock resistance. There is a technique for achieving low water absorption, high strength, and low thermal expansion by increasing the filling amount of the inorganic filler in the resin composition.

  However, when a large amount of an inorganic filler is added to the epoxy resin composition, the melt viscosity of the epoxy resin composition at the time of molding becomes high, the fluidity deteriorates, and problems such as poor filling occur. It is necessary to make the melt viscosity of the composition as low as possible. In order to maintain the melt viscosity of the epoxy resin composition and to increase the inorganic filler, use a filler having a large particle size and a filler having a small particle size, that is, a material having a wide particle size distribution. (Patent Documents 1 to 5: JP-A-3-177450, JP-A-10-158366, JP-A-2001-151988, JP-A-2002-363384, JP-A-2003-12887) Issue gazette). Also known is a method of surface-treating an inorganic filler with a silane coupling agent for the purpose of controlling the interface between the resin used and the inorganic filler in order to lower the melt viscosity of the epoxy resin composition and improve the strength of the cured product. (Patent Documents 6 to 9: JP-A 63-43919, JP-A 9-176278, JP-A 2000-129094, JP-A 2001-261936). However, even in these methods, the decrease in melt viscosity at the time of molding is insufficient and the adhesiveness is also insufficient, and the optimal filler surface treatment agent for achieving both of these methods has not been established. It was the current situation.

JP-A-3-177450 JP-A-10-158366 Japanese Patent Laid-Open No. 2001-151988 JP 2002-363384 A Japanese Patent Laid-Open No. 2003-12887 Japanese Unexamined Patent Publication No. 63-43919 JP-A-9-176278 JP 2000-129094 A JP 2001-261936 A

The present invention has been made in view of the above circumstances. By subjecting an inorganic filler to a surface treatment with a specific compound, the affinity with the resin interface is improved to lower the viscosity, and the substrate and the cured product are effectively produced. a semiconductor encapsulating epoxy resin composition comprising a surface-treated inorganic filler with improved adhesion, and to provide an adhesive and / or a semiconductor device obtained by encapsulating a semiconductor element using the composition Objective.

  As a result of intensive studies to achieve the above object, the inventors of the present invention conducted surface treatment with an inorganic filler containing a compound containing at least one alkoxysilyl group in one molecule and having two or more phenylene skeletons. When the surface-treated inorganic filler obtained by blending into a resin composition such as an epoxy resin composition, it gives good fluidity even when filled at a high level, and the same amount of conventional surface-treated inorganic filler is blended. Compared with the case where it did, it discovered that it had the adhesiveness outstanding while being able to make a composition low viscosity, and came to make this invention.

で示されるいずれかの化合物で表面処理されてなる無機充填材を含むことを特徴とする半導体封止用エポキシ樹脂組成物。
［２］［１］に記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を接着及び／又は封止してなることを特徴とする半導体装置。 Accordingly, the present invention provides a semiconductor encapsulating epoxy resin composition and a semiconductor device below.
[ 1 ] (A) epoxy resin ,
(B) a curing agent ,
(C) a curing accelerator,及Beauty <br/> (D) the following formula

An epoxy resin composition for semiconductor encapsulation, comprising an inorganic filler surface-treated with any of the compounds represented by:
[ 2 ] A semiconductor device obtained by bonding and / or sealing a semiconductor element using the epoxy resin composition for sealing a semiconductor according to [ 1 ].

  The surface-treated inorganic filler of the present invention has good fluidity even when highly filled in a resin composition such as an epoxy resin composition, and has no inconvenience of increasing the viscosity of the resin composition, and has excellent adhesiveness. Have

  In the surface-treated inorganic filler according to the present invention, the type and shape of the filler are not particularly limited as the inorganic filler used as the base material, and it is possible to use all inorganic fillers in a crushed or spherical shape. it can. For example, fused silica powder, spherical silica powder, spherical alumina powder, crystalline silica powder, porous silica powder, secondary agglomerated silica powder or silica powder obtained by pulverizing porous silica powder, alumina powder, talc, silicon nitride, etc. . These inorganic fillers may be used alone or in combination. In general, spherical fused silica powder and spherical alumina powder, which are excellent in balance between flow characteristics, mechanical strength, and thermal characteristics, are preferable.

The average particle size of the inorganic filler is preferably 0.01 to 40 μm, and the maximum particle size is preferably 150 μm or less, and particularly preferably the average particle size is 0.1 to 30 μm and the maximum particle size is 74 μm or less. Moreover, the filling amount can be increased by mixing particles having different particle sizes. Incidentally, the average particle size can be determined as the weight average value D ₅₀ in the particle size distribution measurement by laser diffraction method (or median diameter), and the like. The maximum particle size is a particle size in which the ratio of the remaining amount remaining on the sieve by the wet sieving method is 0, and is measured using a wet sieving shaker (Octagon Model Digital: manufactured by Seishin Enterprise Co., Ltd.). Can do.

  A compound containing at least one, preferably two or more alkoxysilyl groups in one molecule used in the present invention and having two or more phenylene skeletons functions as a surface treatment agent for the inorganic filler. As this compound, it is preferable to use a compound represented by the following general formula (1).

［式中、Ｒ¹は、水素原子、水酸基、ハロゲン原子、アルキル基、アリール基、アラルキル基、アルケニル基、アルコキシ基、アルケニロキシ基、又はグリシジル基，カルボニル基，カルボニロキシ基，シリロキシ基もしくはアルコキシシリル基を含む一価の有機基であるが、Ｒ¹の少なくとも１個はアルコキシシリル基を含む一価の有機基である。ｎは０又は１であり、Ｘは下記の基で示されるものである。

（Ｒ²は、水素原子、ハロゲン原子、アルキル基、アリール基、アラルキル基、アルケニル基又はアルキニル基、ｍは２以上の整数である。）］

[Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a glycidyl group, a carbonyl group, a carbonyloxy group, a silyloxy group or an alkoxysilyl group. In which at least one of R ¹ is a monovalent organic group containing an alkoxysilyl group. n is 0 or 1, and X is represented by the following group.

(R ² is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group or an alkynyl group, and m is an integer of 2 or more.)]

In this case, in R ¹ or R ² , the alkyl group and the alkoxy group have 1 to 10 carbon atoms, preferably 1 to 8, more preferably 1 to 6, and the aryl group has 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Aralkyl groups preferably have 7 to 10 carbon atoms, alkenyl groups, alkynyl groups and alkenyloxy groups preferably have 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. It is preferable that carbon number is 1-12, Preferably it is 2-10, More preferably, it is 2-8.

  Specific examples include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, vinyl group, allyl group, propenyl group, Alkenyl group such as propenyl group, butenyl group, hexenyl group, cyclohexenyl group, aryl group such as phenyl group, tolyl group, xylyl group, aralkyl group such as benzyl group, phenylethyl group, alkynyl group such as ethynyl group, propynyl group , Halogen substitution such as chloromethyl group, cyanoethyl group, 3,3,3-trifluoropropyl group, etc. in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, cyano groups, etc., cyano group-substituted hydrocarbon groups And a group selected from the above. Moreover, as an alkoxy group and an alkenyloxy group, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, methoxyethoxy group, ethoxyethoxy group, vinyloxy group, allyloxy group, propenoxy group, isopropenoxy group And butenyloxy group can be exemplified.

（ｚは１〜６の整数）
が挙げられ、カルボニル基を含む一価の有機基としては、

（Ｒ³は水素原子又はメチル基）
が挙げられる。 As a monovalent organic group containing a glycidyl group,

(Z is an integer from 1 to 6)
As the monovalent organic group containing a carbonyl group,

(R ³ is a hydrogen atom or a methyl group)
Is mentioned.

  The monovalent organic group containing an alkoxysilyl group includes an alkoxysilyl group represented by the following general formula (2), or a hydrogen atom bonded to the terminal carbon atom of an alkylene group having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms. Is preferably substituted with an alkoxysilyl group of the following general formula (2).

（式中、Ｒ⁴、Ｒ⁵は炭素数１〜６のアルキル基、アルケニル基又はアリール基であり、Ｒ⁴、Ｒ⁵は同一であっても異なっていてもよい。ｘは１、２又は３である。）

(In the formula, R ⁴ and R ⁵ are each an alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ may be the same or different. X is 1, 2 or 3)

  In this case, examples of the alkyl group, alkenyl group, and aryl group are the same as those exemplified above.

Examples of such compounds include the following.

  This component is not limited to those having two phenylene groups, and those having three or more phenylene groups can also be used.

  The compounding amount of the alkoxysilyl group and the phenylene skeleton-containing compound in the surface treatment agent component is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the inorganic filler. If the amount is less than 0.01 parts by mass, the effect of addition as a surface treatment agent is small, and the effect of lowering the viscosity of the blended resin composition may be small. If it exceeds 10 parts by mass, the cured product of the blended resin composition may be hard and brittle, or the water absorption rate may increase and solder crack resistance may decrease. A more preferable addition amount is 0.02 to 5 parts by mass, and further preferably 0.05 to 2 parts by mass.

  As the surface treatment method of the inorganic filler in the present invention, an inorganic filler and a compound containing at least one alkoxysilyl group in one molecule and having two or more phenylene skeletons can be mixed uniformly. Then, after the stirring, the surface treatment can be completed by taking it out from the mixer and leaving it at a temperature of room temperature or higher for about 1 day to 1 week. For example, an inorganic filler and a compound containing at least one alkoxysilyl group in one molecule and having two or more phenylene skeletons are put into a mixer such as a ball mill and stirred for 30 minutes to several hours. Thereafter, the surface treatment can be completed by taking it out from the mixer and leaving it at room temperature to 100 ° C. for about 1 day to 1 week.

  Furthermore, a hydrolysis catalyst can be added to complete this surface treatment at high speed. Examples of the hydrolysis catalyst include cycloamidine derivatives such as diazabicycloundecene (DBU), silazanes such as hexamethyldisilazane, organoaluminum compounds such as ammonia, organic amines, and aluminum chelates. Among these, hexamethyldisilazane and ammonia are preferable because they can be easily removed after completion of hydrolysis.

  The addition amount is preferably 0.0001 to 0.5 parts by mass with respect to 100 parts by mass of the inorganic filler. If it is less than 0.0001 part by mass, the catalyst activity is low, and if it exceeds 0.5 part by mass, the remaining hydrolysis catalyst is not preferable because it reduces the moisture resistance of the resin composition.

  Examples of the mixer include blenders such as a ball mill, a Henschel mixer, a V blender, and a double cone blender, a concrete mixer, a ribbon blender, and the like.

  When the surface-treated inorganic filler of the present invention is blended in various resin compositions such as conventionally known sealing materials and adhesive materials, the viscosity is greatly reduced compared to those blended with untreated inorganic filler, When a semiconductor device is sealed with this composition, a semiconductor device excellent in impact resistance reliability, moisture resistance reliability, heat resistance reliability, and crack resistance can be provided. Therefore, the surface-treated inorganic filler of the present invention is suitably used as a filler for a semiconductor sealing resin composition, particularly for a semiconductor sealing epoxy resin composition.

In this case, the epoxy resin composition can be of a known composition,
(A) epoxy resin,
(B) a curing agent,
(C) a curing accelerator,
(D) It can contain an inorganic filler.

  The epoxy resin as the component (A) is not particularly limited. Common examples include novolac type epoxy resins, cresol novolac type epoxy resins, triphenolalkane type epoxy resins, aralkyl type epoxy resins, biphenyl skeleton-containing aralkyl type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, Heterocyclic epoxy resin, naphthalene ring-containing epoxy resin, bisphenol A type epoxy compound, bisphenol F type epoxy compound, stilbene type epoxy resin and the like can be used, and one or more of these can be used in combination. Halogenated epoxy resin is not used.

  The curing agent of component (B) is not particularly limited. Common curing agents include phenol novolac resin, naphthalene ring-containing phenol resin, phenol aralkyl type phenol resin, aralkyl type phenol resin, biphenyl skeleton containing aralkyl type phenol resin, biphenyl type phenol resin, dicyclopentadiene type phenol resin, fat Cyclic phenol resin, heterocyclic phenol resin, naphthalene ring-containing phenol resin, phenol resin such as bisphenol A and bisphenol F, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymix anhydride Acid anhydrides, etc., etc. are mentioned, Among these, 1 type (s) or 2 or more types can be used together.

  Moreover, the compounding quantity ratio of (A) epoxy resin and (B) hardening | curing agent is not restrict | limited in particular, The usage-amount of a hardening | curing agent can be made into the hardening effective amount which hardens an epoxy resin. When the curing agent is a phenol resin, the molar ratio of the phenolic hydroxyl group contained in the (B) curing agent is 0.5 to 1.5 with respect to 1 mole of the epoxy group contained in the (A) epoxy resin. In particular, it is preferably 0.8 to 1.2.

  In the present invention, (C) a curing accelerator is preferably used in order to accelerate the curing reaction between the epoxy resin and the curing agent. The curing accelerator is not particularly limited as long as it accelerates the curing reaction. For example, triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenyl. Phosphorus compounds such as borane, tetraphenylphosphine / tetraphenylborate, tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like can be used. It is preferable that the compounding quantity of a hardening accelerator shall be 0-5 mass parts with respect to a total of 100 mass parts of (A) and (B) component, especially 0.1-5 mass parts.

  In this invention, the said surface treatment inorganic filler is mix | blended as (D) inorganic filler. Of these, the surface-treated silica is preferred. The compounding amount of the surface-treated inorganic filler is 50 to 1,500 parts by mass, more preferably 100 to 1,300 parts by mass, and still more preferably 200 to 1,000 parts by mass with respect to 100 parts by mass of the epoxy resin. can do.

  As long as the object of the present invention is not impaired, inorganic fillers other than the above-mentioned surface treated inorganic fillers, for example, silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide It is optional to add glass fiber or the like.

  The epoxy resin composition of the present invention can further contain various additives as necessary. For example, low stress agents such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicones, waxes such as carnauba wax, higher fatty acids, synthetic waxes, colorants such as carbon black, additives such as halogen trapping agents, etc. It can be added and blended within a range that does not impair the object of the present invention.

  In the epoxy resin composition of the present invention, an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and other additives are blended in a predetermined composition ratio, which is mixed sufficiently uniformly by a mixer or the like, and then heated. Then, a melt mixing process using a kneader, an extruder or the like is performed, followed by cooling and solidification, and pulverization to an appropriate size to obtain a molding material.

  The epoxy resin composition of the present invention thus obtained can be effectively used for sealing various semiconductor devices such as DIP, SOP, QFP, TQFP, TSOP, TSOJ, and BGA. The most common method is a low-pressure transfer molding method. The molding temperature of the epoxy resin composition of the present invention is preferably 150 to 180 ° C. for 30 to 180 seconds, and post-curing is preferably 150 to 180 ° C. for 2 to 16 hours.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a mixture ratio (part) is a mass part.
First, the process inorganic filler used for an Example and a comparative example is shown below.

ヘキサメチルジシラザン０．０５部をスーパーミキサー（株式会社カワタ製のＳＭＶ−２０）にて３，０００ｒｐｍで１０分混合後、乾燥機で１００℃，３時間加熱して処理充填材１を得た。 Treatment filler 1
100 parts of true spherical silica (average particle size 0.5 μm, specific surface area 6 m ² / g), 1.0 part of a compound represented by the following formula (3),

After mixing 0.05 parts of hexamethyldisilazane with a super mixer (SMV-20 manufactured by Kawata Co., Ltd.) at 3,000 rpm for 10 minutes, the treated filler 1 was obtained by heating at 100 ° C. for 3 hours with a dryer. .

ＤＢＵ０．００５部をスーパーミキサー（株式会社カワタ製のＳＭＶ−２０）にて３，０００ｒｐｍで１０分混合後、室温にて３日間密閉容器で保管して処理充填材２を得た。 Treatment filler 2
100 parts of true spherical silica (average particle size 0.5 μm, specific surface area 6 m ² / g), 1.0 part of a compound represented by the following formula (4),

0.005 parts of DBU was mixed with a super mixer (SMV-20 manufactured by Kawata Co., Ltd.) at 3,000 rpm for 10 minutes, and then stored in a sealed container at room temperature for 3 days to obtain a treated filler 2.

Treatment filler 3
100 parts of true spherical alumina (average particle size 10 μm, specific surface area 1.5 m ² / g), 1.0 part of the compound represented by the above formula (3) and 0.05 part of hexamethyldisilazane were added to a super mixer (Co., Ltd. After mixing for 10 minutes at 3,000 rpm with SMV-20) manufactured by Kawata, the treated filler 3 was obtained by heating at 100 ° C. for 3 hours with a dryer.

Treatment filler 4
100 parts of true spherical silica (average particle size 0.5 μm, specific surface area 6 m ² / g), 1.0 part of γ-glycidoxypropyltrimethoxysilane, 0.05 part of hexamethyldisilazane were added to a super mixer (Kawata Corporation). SMV-20) manufactured at 3,000 rpm for 10 minutes, and then heated at 100 ° C. for 3 hours with a dryer to obtain treated filler 4.

[Examples 1 to 3, Comparative Example 1]
58 parts of liquid bisphenol A type epoxy resin (RE-310S: manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, 42 parts of methyltetrahydrophthalic anhydride (MH-700: manufactured by Shin Nippon Chemical Co., Ltd.) as a curing agent, and DBU-based tetra as a curing accelerator 1.0 part of phenylborate salt (U-CAT5002: manufactured by San Apro), 1.0 part of γ-glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and Table 1 as a processing filler The amount to be described was uniformly mixed with a mixer (AR-250, manufactured by Sinky) to obtain an epoxy resin composition for semiconductor encapsulation. The viscosities at 25 ° C. of these compositions were measured with a rotational viscometer. Further, using these compositions, the copper plate and the silicon plate were bonded at 150 ° C. for 6 hours, and the shear adhesive force was measured. The results are shown in Table 1.

From the results shown in Table 1, the composition of the present invention has a low viscosity, has a good moldability, and has a high adhesion, whereby a highly reliable semiconductor device can be obtained.

Claims (2)

(A) epoxy resin ,
(B) a curing agent ,
(C) a curing accelerator,及Beauty <br/> (D) the following formula

An epoxy resin composition for semiconductor encapsulation, comprising an inorganic filler surface-treated with any of the compounds represented by: A semiconductor device comprising a semiconductor element bonded and / or sealed using the epoxy resin composition for semiconductor sealing according to claim 1 .