JP2000273326A - Liquid resin composition and semiconductor device using the same - Google Patents

Abstract

(57) [Problem] To provide a highly reliable liquid resin composition exhibiting good moisture adhesion and excellent solder reflow resistance regardless of whether an adherend is a metal such as a lead frame or an organic substrate. And a highly reliable semiconductor device. SOLUTION: A filler (A), a thermosetting resin (B) which is liquid at normal temperature, at least one amino group having active hydrogen in one molecule, and at least one functional group represented by the following formula (1). And a liquid resin composition comprising a compound (C) having a carbon-carbon double bond, wherein the compound (C)
Is a liquid resin composition containing 0.05 wt% to 5 wt% in the whole resin. A semiconductor device using the liquid resin composition. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid resin composition for bonding a semiconductor element such as an IC or an LSI to a metal frame, an organic substrate or the like.

[0002]

2. Description of the Related Art With the remarkable development of the electronics industry in recent years, the degree of integration of circuits in transistors, ICs, LSIs, VLSIs and semiconductor devices has been rapidly increasing.
For this reason, the size of the semiconductor element has been dramatically increased from about several mm in the past to about several tens of mm, and the number of pins electrically connected to the outside to increase the speed of the semiconductor element is also two.
It is over the 00 pin. Also, in the mounting of semiconductor products, higher density, thinner, and higher speed are further accelerated, and as a result, the semiconductor products themselves are not limited to conventional packages such as QFP, but also to BGA and other surfaces. With the emergence of mounting type packages, packages are becoming thinner.

[0003] Under such a trend, a die attach material for bonding a semiconductor element to a lead frame or an organic substrate is required to have higher adhesiveness than ever before. Metal plating, the surface of an organic substrate, and the surface of a solder mask are various, and there are many cases where these are used alone or in combination.

[0004] Therefore, the die attach material is required to have excellent adhesion to various surfaces, and particularly to a very good moisture resistance adhesion resistance to withstand the thermal stress generated during the soldering process when the package has absorbed moisture. . However, some conventional die attach materials showed good adhesion to a specific adherend, but none showed good results for a wide variety of surfaces. There was no one that could not withstand the thermal stress during the treatment, or even if it could, only a specific package could handle various adherend surfaces and thus various packages.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a highly reliable liquid having excellent moisture adhesion and excellent solder reflow resistance regardless of whether the adherend is a metal such as a lead frame or an organic substrate. It is to provide a highly reliable semiconductor device by providing a resin composition, and by using the liquid resin composition of the present invention.

[0006]

The filler (A), the thermosetting resin (B) which is liquid at room temperature, and at least one amino group having active hydrogen in one molecule are represented by the following formula (1). A liquid resin composition comprising a compound (C) having at least one functional group and a carbon-carbon double bond, wherein the compound (C) is present in the entire resin in an amount of 0.05 wt% to 5 wt%.
% Of the liquid resin composition.

Embedded image

More preferably, the compound (C) is a compound obtained by reacting N-phenyl-γ-aminopropyltrimethoxysilane with alkenylsuccinic anhydride, or N-phenyl-γ-aminopropyltrimethoxysilane. It is a liquid resin composition that is a compound obtained by reacting methoxysilane with dodecenyl succinic anhydride. A semiconductor device manufactured using the above liquid resin composition as a die attach material.

Since the filler (A) used in the present invention is used in a semiconductor field, the content of ionic impurities such as halogen ions and alkali metal ions is preferably 10 ppm or less. Depending on the required characteristics, metal fillers such as silver, gold, copper and nickel, inorganic fillers such as silica, aluminum nitride and boron nitride, or organic fillers such as calcined phenol particles and polyimide particles can be used alone or in combination. Flake, fibrous, resinous, amorphous or spherical shapes can be used alone or in combination. Further, with respect to the particle size, usually, the average particle size is preferably 2 to 10 μm and the maximum particle size is preferably about 50 μm, and a mixture of a relatively fine filler and a coarse filler may be used.

The resin component used in the present invention is limited to the thermosetting resin (B) which is liquid at room temperature. However, if the resin is not a liquid resin at room temperature, a solvent is required for kneading with the filler. The solvent is not preferable because it causes bubbles, particularly when the chip size is large, and lowers the adhesive strength and thermal conductivity of the cured product. If the resin used is not thermosetting, a resin having a high molecular weight must be used in advance to obtain sufficient adhesive strength, or a reaction initiated by energy other than heat must be used. Use of a resin is not preferred because a solvent is required.

The reaction by energy other than heat is known to utilize electromagnetic waves such as ultraviolet rays, X-rays, and microwaves. However, since the liquid resin composition is used for bonding a substrate to a semiconductor element, the liquid resin composition is used for the purpose. However, the use of electromagnetic waves that are opaque to silicon is not practical.

Examples of the thermosetting resin which is liquid at room temperature include, for example, a mixture of an epoxy resin and a curing agent which is liquid at room temperature, and a mixture of an acrylate resin or / and a methacrylate resin and a curing initiator which is liquid at room temperature. And a mixture of a cyanate ester resin, an epoxy resin and a curing accelerator which is liquid at ordinary temperature.

In the present invention, the compound (C) having at least one amino group having active hydrogen in one molecule, at least one functional group represented by the formula (1), and a carbon-carbon double bond is used. 0.05 wt% to 5 wt% is used in all resins.

Usually, an adhesion aid such as a silane coupling material is generally used to improve the adhesion. For example, when the silane coupling material is added to the liquid resin composition without any treatment, In many cases, the desired effect is not exhibited due to evaporation during heating and curing, and there is a high risk that gas components generated during curing may contaminate the die surface, the lead frame or the substrate surface. Contamination leads to a decrease in adhesion of the sealing resin, leading to a decrease in reliability. In addition, the method of preliminarily treating a filler or the like generally increases the cohesive force of the cured product itself, which leads to the improvement of the adhesion strength, but does not contribute much to the improvement of the adhesion at the interface with the adherend. Deterioration of adhesion strength due to processing is large.

In the present invention, a compound (C) having at least one amino group having active hydrogen in one molecule, at least one functional group represented by the formula (1) and a carbon-carbon double bond is used. This is because, first, the polarity of the amino group having active hydrogen contributes to high adhesion, second, the functional group represented by the formula (1) contributes to adhesion to the substrate or chip, and third, It is based on the fact that the introduction of the carbon-carbon double bond contributes to a great improvement in the adhesiveness particularly to the surface of the cured solder resist.

Preferably, the compound (C) of the present invention is
A compound obtained by reacting -phenyl-γ-aminopropyltrimethoxysilane with alkenylsuccinic anhydride, or a compound obtained by reacting N-phenyl-γ-aminopropyltrimethoxysilane with dodecenylsuccinic anhydride. Adhesion is further improved by using these compounds.

In the present invention, the compounding ratio of the compound (C) is
It is 0.05 wt% to 5 wt% based on the liquid resin composition. When the amount is less than 0.05 wt%, the expected effect of improving the moisture absorption and adhesion is not exhibited. When the amount is more than 5 wt%, the viscosity of the liquid resin composition becomes too high, and the workability of coating is deteriorated, or This is because the amount of the functional group represented by the formula (1) becomes too large, and voids based on the generated alcohol are observed, which is not preferable.

The production method of the present invention includes, for example, preliminarily mixing the components, kneading them using a three-roll mill, kneading the mixture, and defoaming under vacuum to obtain a resin paste.

[0018]

The present invention will be specifically described below with reference to examples. The mixing ratio is shown in parts by weight. <Examples 1 to 3> Flaky silver powder (hereinafter referred to as silver powder) having a particle diameter of 1 to 30 μm and an average particle diameter of 3 μm, diglycidyl bisphenol A obtained by the reaction of bisphenol A with epichlorohydrin (epoxy equivalent 180, liquid at room temperature, Bis-A epoxy), cresyl glycidyl ether (epoxy equivalent 185), phenol novolak (hydroxyl equivalent 104, softening point 80-90 ° C.), dicyandiamide, diazabicycloundecene and 49 g weighed in a three-neck separable flask. While stirring N-phenyl-γ-aminopropyltrimethoxysilane at 200 rpm, 51 g of dodecenylsuccinic anhydride was added using a dropping funnel in 10 minutes, and the compound obtained by reacting for 12 hours (hereinafter referred to as Compound D) was added to Mix in the ratio shown in the table, knead with three rolls To obtain a composition. The internal temperature during the reaction reached its maximum 11 minutes after the start of the addition, and rose to 38 ° C. This liquid resin composition is placed in a vacuum chamber at 2 mmH
After degassing for 30 minutes with g, various performances were evaluated by the following methods.

Viscosity: The viscosity was measured by using an E-type viscometer (3 ° cone) at 25 ° C. and 2.5 rpm to determine the viscosity. -Storage property at room temperature: After standing at 25 ° C for 48 hours, the viscosity was measured by the above method, and the case where the rate of change of the obtained value with respect to the initial value was 20% or less was regarded as acceptable. Adhesive strength (1): A 6 × 6 mm silicon chip was mounted on a copper frame using a liquid resin composition and cured in an oven at 150 ° C. for 60 minutes. After curing, the die shear strength under heat at 250 ° C. was measured using an automatic mount strength measuring device (DAGE PC-2400). The cured sample was subjected to a water absorption treatment at 85 ° C. and 85% for 72 hours, and the hot die shear strength at 250 ° C. was measured.・ Adhesive strength (2): A silicon chip of 6 × 6 mm is formed using a liquid resin composition on an organic substrate (solder mask: solar ink PSR-4000AUS5 / CA-40AUS2).
And cured in a 150 ° C. oven for 60 minutes. The adhesive strength was measured in the same manner as the adhesive strength after curing (1).

Example 4 A liquid resin composition was prepared and evaluated in the same manner as in Examples 1 to 3, except that crushed silica (average particle size: 3 μm, maximum particle size: 16 μm or less) was used as a filler.

<Comparative Examples 1 to 5> Conductive resin pastes were prepared in exactly the same manner as in the examples with the mixing ratios shown in Table 1. In Comparative Examples 3 and 4, N-phenyl-γ-aminopropyltrimethoxysilane and dodecenylsuccinic anhydride were used alone, and in Comparative Example 5, N-phenyl-γ-aminopropyltrimethoxysilane and methyltetrahydrophthalic anhydride were used. Reaction product (Compound E: 69.7 g of N-phenyl-γ-aminopropyltrimethoxysilane weighed in a three-neck separable flask was stirred at 200 rpm, and 39.7 g of methyltetrahydrophthalic anhydride was added dropwise to the funnel. A compound obtained by adding for 10 minutes and reacting for 12 hours was used, and the internal temperature during the reaction reached its maximum at 15 minutes after the start of the addition and rose to 42 ° C.).

Table 1 shows the evaluation results.

[Table 1]

[0023]

As described above, the liquid resin composition of the present invention is excellent in moisture absorption adhesion to an organic substrate coated with a solder mask as well as a metal frame made of copper, 42 alloy or the like. This is a highly reliable liquid resin composition for bonding a semiconductor element, which has never existed before and does not generate cracks during processing.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Onoguchi 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F term (reference) 4J002 BG031 CC032 CD001 CE001 CM042 DA066 DF016 DK006 EX017 EX077 FD012 FD016 5F047 AA02 AA07 AA11 AA17 BA23 BA24 BA34 BA51 BA52 BB11 BB16

Claims (4)

[Claims] 1. A filler (A), a thermosetting resin (B) which is liquid at normal temperature, at least one amino group having active hydrogen in one molecule, and at least a functional group represented by the following formula (1): A liquid resin composition comprising one compound and a compound (C) having a carbon-carbon double bond, wherein the compound (C)
Is contained in the entire resin in an amount of 0.05 wt% to 5 wt%. Embedded image 2. The method according to claim 1, wherein the compound (C) is N-phenyl-γ-
The liquid resin composition according to claim 1, which is a compound obtained by reacting aminopropyltrimethoxysilane with alkenylsuccinic anhydride. 3. The method according to claim 1, wherein the compound (C) is N-phenyl-γ-
The liquid resin composition according to claim 1, which is a compound obtained by reacting aminopropyltrimethoxysilane with dodecenylsuccinic anhydride. 4. A semiconductor device manufactured using the liquid resin composition according to claim 1 as a die attach material.