JP4317432B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same - Google Patents

Description

  The present invention relates to an epoxy resin composition for semiconductor encapsulation excellent in moldability and curability and a semiconductor device using the same.

  Conventionally, semiconductor elements such as transistors, ICs, and LSIs are sealed using a plastic package, for example, a thermosetting epoxy resin composition, from the viewpoint of enabling protection from the external environment and handling of the semiconductor elements. It is made into a semiconductor device.

  The thermosetting epoxy resin composition is generally blended with a curing accelerator in order to accelerate the curing reaction of the resin during molding. Examples of the epoxy resin curing accelerator include nitrogen-containing heterocyclic compounds such as amines, imidazole compounds, 1,8-diazabicyclo (5,4,0) undecene-7, phosphine compounds, A quaternary ammonium compound, a phosphonium compound, an arsonium compound, or the like is used.

  Usually, the epoxy resin composition containing these curing accelerators is compounded and designed so that the reaction occurs rapidly under the high temperature conditions at the time of molding and the curing is completed within a short time. For this reason, the curing reaction may start before the epoxy resin composition is completely filled into the molding die cavity during molding. In such a situation, the resin viscosity increases or the fluidity decreases. In terms of moldability, such as deformation of bonding wires connecting semiconductor elements and external terminals such as lead frames, defects such as contact between adjacent bonding wires, or cutting of bonding wires, and defects such as unfilled resin Serious malfunction may occur.

As a method for avoiding such a problem, for example, a method of delaying the start of the curing reaction by using a microcapsule type curing accelerator is employed (see Patent Document 1).
JP-A-10-168164

  However, the above-described method has a problem that the productivity is greatly lowered due to the slow progress of the curing reaction, and the hardness and strength of the cured product itself are insufficient.

  This invention is made | formed in view of such a situation, The objective is to provide the epoxy resin composition for semiconductor sealing excellent in moldability and sclerosis | hardenability, and a semiconductor device using the same.

In order to achieve the above object, the first gist of the present invention is an epoxy resin composition for semiconductor encapsulation containing the following components (A) to (D).
(A) Epoxy resin.
(B) Phenolic resin.
(C) A tetra-substituted phosphonium-phenol resin salt compound represented by the following general formula (1) having a softening point in the range of 100 to 200 ° C.
(D) Inorganic filler.

  And this invention makes the 2nd summary the semiconductor device formed by resin-sealing a semiconductor element using the said epoxy resin composition for semiconductor sealing.

  That is, the present inventors have intensively studied in order to obtain an epoxy resin composition that causes an appropriate curing reaction and becomes a sealing material having excellent moldability. In the process, we focused on the curing accelerator itself, which is used as a compounding material and greatly contributes to the curing reaction, and researched mainly on compounds that act as a curing accelerator. As a result, when a tetra-substituted phosphonium-phenol resin salt compound having a softening point in a specific range represented by the general formula (1) as a curing accelerator is used, it can be controlled to an appropriate curing reaction and good curability is obtained. As a result, the present inventors have found that excellent fluidity can be obtained.

  As described above, the present invention is an epoxy resin composition for encapsulating a semiconductor using the specific tetra-substituted phosphonium-phenol resin salt compound [(C) component] represented by the general formula (1). . For this reason, good fluidity is imparted with an appropriate curing reaction, and excellent moldability and curability are obtained. Therefore, the semiconductor device obtained using the epoxy resin composition for semiconductor encapsulation of the present invention is excellent in reliability without problems such as deformation and cutting of the bonding wire in the package.

  And if the epoxy resin which has a biphenyl group is used as an epoxy resin, the improvement of the further reliability by the moisture absorption reduction of hardened | cured material will be aimed at.

  The epoxy resin composition for semiconductor encapsulation of the present invention uses an epoxy resin (A component), a phenol resin (B component), a specific curing accelerator (C component), and an inorganic filler (D component). Usually, it is in the form of a powder or a tablet obtained by tableting this.

  The epoxy resin (component A) used in the present invention is not particularly limited, and a compound having two or more epoxy groups in one molecule is used. For example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more. Among these epoxy resins, it is preferable from the viewpoint of reliability to use a biphenyl type epoxy resin or a low moisture absorption type epoxy resin in which a lower alkyl group is added to the phenyl ring. Such an epoxy resin preferably has an epoxy equivalent of 150 to 250 and a softening point or melting point of 50 to 130 ° C.

  The phenol resin (component B) used together with the epoxy resin (component A) serves as a curing agent for the epoxy resin, and is not particularly limited, and two or more phenolic hydroxyl groups in one molecule. Monomers, oligomers, and polymers in general. Examples thereof include phenol novolak, cresol novolak, biphenyl type novolak, triphenylmethane type, naphthol novolak, phenol aralkyl resin, biphenyl aralkyl resin and the like, and these are used alone or in combination of two or more. Among them, it is preferable from the viewpoint of reliability to use a low hygroscopic material such as a phenol aralkyl resin or a biphenyl aralkyl resin.

  The blend ratio of the epoxy resin (component A) and the phenol resin (component B) is blended so that the hydroxyl group equivalent in the phenol resin is 0.5 to 2.0 equivalents per equivalent of epoxy group in the epoxy resin. It is preferable. More preferably, it is 0.8-1.2 equivalent.

  The specific curing accelerator (C component) used together with the A component and the B component is a specific tetra-substituted phosphonium-phenol resin salt compound represented by the following general formula (1). By using an agent (component C), an epoxy resin composition for semiconductor encapsulation excellent in moldability and curability can be obtained.

  And the tetra substituted phosphonium-phenol resin salt compound (C component) represented by the said General formula (1) has what has various softening points by adjusting the structure and molecular weight of the said phenol resin part. Among them, as in the present invention, those having a softening point of 100 ° C. or higher have low solubility in epoxy resins and phenol resins. The component or component B is not uniformly mixed at the molecular level, and is incompatible with each other. For this reason, the curing reaction as an epoxy resin composition hardly proceeds in the state after the melt kneading, and the curing reaction proceeds only at a high temperature state at the time of molding. Therefore, since the timing of starting curing is delayed as compared with the case of using other commonly used catalyst systems (curing accelerators), so-called potential is exhibited. Thus, the softening point of the tetra-substituted phosphonium-phenol resin salt compound (C component) represented by the general formula (1) showing the potential must be set within a range of 100 to 200 ° C., preferably Is in the range of 120-170 ° C. That is, when the softening point is less than 100 ° C., the C component and the A component or the B component are uniformly mixed at the molecular level during the melt kneading, and the curing reaction at a low temperature tends to proceed. On the other hand, when the softening point exceeds 200 ° C., the compatibility between the component C and the component A or component B is remarkably deteriorated, and good curability cannot be exhibited in a short time during molding.

Thus, represented by the general formula (1), tetra-substituted phosphonium having a specific softening point - The phenol resin salt compound (C component), specifically, Application Benefits phenylmethyl phosphonium ions - phenol novolak resin Salt .

  And the tetra substituted phosphonium-phenol resin salt compound (C component) which has a specific softening point represented by the said General formula (1) can be manufactured as follows, for example. That is, it can be produced by reacting a tetra-substituted phosphonium halide and a phenol novolac resin at a predetermined ratio in the presence of a basic catalyst.

  The content of the specific curing accelerator (component C) is preferably set in the range of 1 to 20 parts with respect to 100 parts by weight (hereinafter abbreviated as “part”) of the phenol resin (component B). Preferably it is 2-15 parts. That is, if it is less than 1 part, the curing reaction between the target epoxy resin (component A) and the phenol resin (component B) is difficult to proceed, so it becomes difficult to obtain sufficient curability. This is because the reaction tends to be too fast and the moldability tends to be impaired.

  Moreover, in this invention, you may use together conventionally well-known various hardening accelerators in the range which does not impair the characteristic of this invention with the said specific hardening accelerator (C component). Examples of the conventionally known various curing accelerators include triarylphosphines, tetraphenylphosphonium / tetraphenylborate, imidazoles such as 2-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7. Etc. These may be used alone or in combination of two or more. In addition, when using the said conventionally well-known various hardening accelerator together, specifically, it is preferable to set content of this various hardening accelerator to 50 weight% or less of the whole hardening accelerator component.

  It does not specifically limit as an inorganic filler (D component) used with the said AC component, Various conventionally well-known fillers are used. Examples thereof include silica powder such as fused silica powder and crystalline silica powder, alumina powder, talc and the like. These inorganic fillers can be used in any form such as crushed, spherical, or ground. Of these, spherical fused silica powder is preferably used. And these inorganic fillers are used individually or in combination of 2 or more types. As said inorganic filler (D component), it is preferable to use a thing with the average particle diameter of the range of 5-40 micrometers from the point of making fluidity | liquidity favorable. The average particle size can be measured, for example, with a laser diffraction / scattering particle size distribution analyzer.

  And it is necessary to set content of the said inorganic filler (D component) in the range of 70 to 95 weight% of the whole epoxy resin composition. Especially preferably, it is the range of 85-92 weight%. That is, if it is less than 70% by weight, the viscosity of the epoxy resin composition becomes too low, resulting in poor appearance (void) at the time of molding. This is because it occurs.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, in addition to the above components A to D, pigments such as silane coupling agents, flame retardants, flame retardant aids, mold release agents, ion trap agents, carbon black, etc. And other additives such as coloring agents, stress reducing agents, tackifiers and the like can be appropriately blended.

  The silane coupling agent is not particularly limited, and various silane coupling agents can be used. Among them, those having two or more alkoxy groups are preferably used. Specifically, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxy Examples thereof include silane, γ-mercaptopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, and hexamethyldisilazane. These may be used alone or in combination of two or more.

  Examples of the flame retardant include novolak-type brominated epoxy resins and metal hydroxides, and examples of the flame retardant aid include diantimony trioxide and diantimony pentoxide. These may be used alone or in combination of two or more.

  Examples of the releasing agent include compounds such as higher fatty acids, higher fatty acid esters, higher fatty acid calcium, and the like. For example, carnauba wax and polyethylene wax are used, and these are used alone or in combination of two or more.

  As said ion trap agent, all the well-known compounds which have ion trap ability can be used, for example, hydrotalcites, bismuth hydroxide, etc. are used.

  Examples of the stress reducing agent include butadiene rubbers such as methyl acrylate-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer, and silicone compounds.

  The epoxy resin composition for semiconductor encapsulation of the present invention can be produced, for example, as follows. That is, after mixing and mixing the above components A to D and other additives as required, the mixture is melted and mixed in a heated state in a kneader such as a hot roll or a kneader, cooled to room temperature, and then known means. Can be produced by a series of steps of pulverizing and tableting as necessary.

  The sealing of the semiconductor element using such an epoxy resin composition is not particularly limited, and can be performed by a known molding method such as normal transfer molding.

  Next, examples will be described together with comparative examples.

  First, the following components were prepared prior to the examples.

〔Epoxy resin〕
Biphenyl type epoxy resin (epoxy equivalent 192, melting point 105 ° C)

[Phenolic resin a]
Biphenyl aralkyl type phenolic resin (hydroxyl equivalent 203, softening point 65 ° C)

[Phenolic resin b]
Phenol novolac resin (hydroxyl equivalent 104, softening point 60 ° C)

[Curing accelerator a]
Triphenylmethylphosphonium ion-phenol novolac resin salt (softening point 101 ° C.)

[Curing accelerator b]
Triphenylmethylphosphonium ion-phenol novolak resin salt (softening point 131 ° C.)

[Curing accelerator c]
Triphenylmethylphosphonium ion-phenol novolak resin salt (softening point 143 ° C.)

[Curing accelerator d]
Triphenylmethylphosphonium ion-phenol novolak resin salt (softening point 190 ° C)

[Curing accelerator e]
Triphenylmethylphosphonium ion-phenol novolak resin salt (softening point 90 ° C)

[Curing accelerator f]
Triphenylmethylphosphonium ion-phenol novolak resin salt (softening point 210 ° C.)

[Curing accelerator g]
Triphenylphosphine

[Curing accelerator h]
Tetraphenylphosphonium ・ tetraphenylborate

[Inorganic filler]
Spherical fused silica powder (average particle size 13μm)

[Pigment]
Carbon black

〔Flame retardants〕
Magnesium hydroxide

〔Silane coupling agent〕
3-Methacryloxypropyltrimethoxysilane

〔Release agent〕
Oxidized polyethylene wax

[Examples 1-8, Comparative Examples 1-4]
The raw materials shown in Tables 1 and 2 below were blended in the proportions shown in the same table and mixed thoroughly with a mixer, and then melt kneaded at 100 ° C. for 2 minutes using a biaxial kneader. Next, the melted product was cooled and then pulverized to produce a desired powdery epoxy resin composition. In Comparative Example 2, tetraphenylphosphonium tetraphenylborate which is a curing accelerator, biphenylaralkyl type phenol resin and phenol novolac resin were preliminarily mixed at 180 ° C. for 1 hour, and then this premixed mixture and the rest Then, the blended components were sufficiently mixed with a mixer, and then melt kneaded at 100 ° C. for 2 minutes using a biaxial kneader. And after cooling this melt, the target powdery epoxy resin composition was produced by grind | pulverizing.

  Using the obtained epoxy resin compositions, characteristics (gelation time, curing rise time, hot hardness) were measured and evaluated according to the following methods. Moreover, the semiconductor device was manufactured using each said epoxy resin composition, and the condition of the gold wire flow at this time was measured and evaluated according to the following method. These results are shown in Tables 3 to 4 below.

[Gelification time]
The time until the epoxy resin composition was melted and gelled on a hot plate at 175 ° C. was measured.

[Curing rise time]
Using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type), at the point where the torque value reached 0.02 N · m at a die temperature of 175 ° C., an amplitude of ± 1 °, and a vibration frequency of 100 cpm. It was time.

[Hardness during heating]
Molding was performed at a mold temperature of 175 ° C. and a curing time of 90 seconds, and the value of Shore D hardness measured using a Shore D hardness meter after 10 seconds of mold opening was taken as the hot hardness. That is, it can be said that the higher the value of the hardness at heat, the better the curability.

[Gold wire flow]
Using the epoxy resin compositions obtained in the above examples and comparative examples, LQFP-144 (size: 20 mm × 20 mm × thickness 1.4 mm) with a gold wire (wire diameter 23 μm, wire length 6 mm), A semiconductor device was obtained by molding (condition: 175 ° C. × 90 seconds) with an automatic molding machine (CPS-40L) manufactured by TOWA and post-curing at 175 ° C. × 5 hours. That is, at the time of manufacturing the semiconductor device, as shown in FIG. 1, a gold wire 2 is stretched on an LQFP package frame having a die pad 1, and this is used to seal the resin with the epoxy resin composition to manufacture a package. did. In FIG. 1, 3 is a semiconductor chip and 4 is a lead pin. And the produced wire package was measured for the amount of gold wire flow using a soft X-ray analyzer. The measurement was performed by selecting 10 wire wires from each package and measuring the flow amount of the gold wire 2 from the front direction as shown in FIG. And the value which becomes the maximum part of the flow quantity of the gold wire 2 was made into the value (dmm) of the gold wire flow quantity of the package, and gold wire flow rate [(d / L) * 100] was computed. L indicates the distance (mm) between the gold wire 2. And the thing with the said gold wire flow rate of 6% or more was displayed as x, and the thing below 6% was displayed as (circle).

  From the above results, the product of the example had an appropriate curing rise time, high thermal hardness, and good results with respect to gold wire flow. From this, it can be seen that the example products are excellent in both moldability and curability.

  On the other hand, Comparative Examples 1 and 2 blended with conventional curing accelerators had both a short gelation time and a curing rise time, and a low heat hardness. Furthermore, inferior results were obtained with respect to gold wire flow. Moreover, among the comparative examples 3 and 4 using the curing accelerators e and f whose softening point was out of the range of 100 to 200 ° C., the comparative example 3 had high heat hardness, but the wire wire flow It was inferior to. Moreover, although the comparative example 4 goods had the favorable gold | metal wire flow, the hardness at the time of heat was low and sclerosis | hardenability was also bad.

It is a front view which shows the package used in order to measure the amount of gold | metal wire flow of a semiconductor device. It is a schematic diagram which shows the measuring method of the gold wire wire flow rate of a semiconductor device.

Claims (3)

The epoxy resin composition for semiconductor sealing characterized by containing the following (A)-(D) component.
(A) Epoxy resin.
(B) Phenolic resin.
(C) A tetra-substituted phosphonium-phenol resin salt compound represented by the following general formula (1) having a softening point in the range of 100 to 200 ° C.
(D) Inorganic filler.   The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the epoxy resin as the component (A) is an epoxy resin having a biphenyl group.   A semiconductor device obtained by resin-sealing a semiconductor element using the epoxy resin composition for semiconductor encapsulation according to claim 1.