JPH05259313A - Semiconductor device - Google Patents

Abstract

PURPOSE:To improve moistureproof reliability, heat-resistant reliability and mechanical strength by conducting resin sealing by using a special resin composition containing a specific polymaleimido compound, a special polynuclear aromatic carboxylic acid allyl ester compound and a curing catalyst. CONSTITUTION:A semiconductor element is resin-sealed by a resin composition comprising (A)-(C) components. (A) a maleimido compound having two or more of maleimido groups in one molecule. (B) a polynuclear aromatic carboxylic acid allyl ester compound of one or more of formulae I-III. (in formula, R represents phenylene or a 1-3C hydrocarbon group, at least one of R<1>-R<5> -COO- CH2-CH=CH2 and others the 1-3C hydrocarbon group. (n) is 0 or 1.) (C) a curing catalyst. The resin composition is used for resin seal, thus reducing internal stress, then improving moistureproof reliability, heat-resistant reliability and mechanical strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device having excellent reliability.

[0002]

2. Description of the Related Art Semiconductor elements such as transistors, ICs, and LSIs are usually sealed by a ceramic package or a plastic package to form a semiconductor device. In the above ceramic package, since the constituent material itself has heat resistance and excellent moisture permeability,
It is highly resistant to humidity, and because of its hollow package, it has high mechanical strength and enables highly reliable sealing. However, since the constituent materials are relatively expensive and have the drawback of being inferior in mass productivity, resin sealing using the plastic package has recently become the mainstream. An epoxy resin composition has been conventionally used for this type of resin encapsulation, and has achieved good results. However, due to technological innovations in the semiconductor field, the degree of integration has improved, the device size has become larger, and the wiring has become finer, resulting in a smaller package.
There is a tendency to reduce the thickness, and along with this there is a demand for further improvement in the reliability of the encapsulation material (internal stress, moisture resistance reliability, shock resistance reliability, heat resistance reliability, etc. of the resulting semiconductor device). Has been done.

In recent years, a maleimide resin, which is superior in heat resistance to epoxy resin (glass transition temperature 100 to 200 ° C.), as a sealing resin for semiconductor elements in order to obtain such high reliability, particularly high heat resistance reliability. (Glass transition temperature 200
Various systems using (~ 300 ° C) have been studied.

[0004]

However, the above maleimide resin has a drawback that it is hard and brittle because the cured product thereof has a higher elastic modulus and a lower energy absorption capacity than the epoxy resin. Further, when the maleimide resin is used as the sealing resin, there is a problem that the moisture resistance reliability is insufficient.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a semiconductor device having high reliability with excellent moisture resistance reliability, heat resistance reliability, and mechanical strength.

[0006]

In order to achieve the above object, the semiconductor device of the present invention encloses a semiconductor element with a resin composition containing the following components (A) to (C). Take composition. (A) A maleimide compound having two or more maleimide groups in one molecule. (B) At least one polycyclic aromatic carboxylic acid allyl ester compound selected from the group consisting of polycyclic aromatic carboxylic acid allyl ester compounds represented by the following general formulas (1), (2) and (3) ..

[Chemical 7]

[Chemical 8]

[Chemical 9] (C) Curing catalyst.

[0007]

FUNCTIONS That is, the present inventors have conducted a series of studies in order to obtain a sealing resin having excellent reliability. As a result, it was found that excellent reliability can be obtained by using a maleimide compound as a main component and using the above-mentioned special polycyclic aromatic carboxylic acid allyl ester compound as a substance having a curing agent action of this maleimide compound. Reached

Next, the present invention will be described in detail.

The resin composition used in the present invention comprises a specific maleimide compound (A component), a special polycyclic aromatic carboxylic acid allyl ester compound (B component) and a curing catalyst (C component). It is obtained, and is usually in the form of powder or a tablet formed by compressing it.

The specific maleimide compound (component A) has two or more maleimide groups in one molecule and is represented by, for example, the following general formulas (4), (5) and (6). And a maleimide compound obtained by using the same.

[Chemical 10]

[0011]

[Chemical 11]

[0012]

[Chemical 12]

These maleimide compounds may be used alone or in combination.

An epoxy resin may be used as a part of the maleimide compound (component A). The epoxy resin is not particularly limited, and examples thereof include conventionally known various compounds having two or more epoxy groups in one molecule. For example, usually, an epoxy equivalent of 50 to 500
0, those having a softening point of room temperature to 200 ° C. are preferred, and those having an epoxy equivalent of 100 to 3000 and a softening point of room temperature to 150 ° C. are particularly preferred. Such epoxy resins include those that are liquid at room temperature and those that are solid at room temperature. Specifically, glycidyl ethers of phenols such as bisphenol A type, bisphenol F type, resorseal, phenol novolac and cresol novolac,
Examples thereof include glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol.

The special polycyclic aromatic carboxylic acid allyl ester compound (component B) used together with the specific maleimide compound (component A) acts as a curing agent for the specific maleimide compound (component A), The following general formulas (1), (2) and (3) are listed, and they may be used alone or in combination.

[0016]

[Chemical 13]

[0017]

[Chemical 14]

[0018]

[Chemical 15]

The above-mentioned special polycyclic aromatic carboxylic acid allyl ester compound is obtained by esterifying the polycyclic aromatic carboxylic acid and allyl alcohol or the polycyclic aromatic carboxylic acid and allyl halide. The production method is a conventionally known production method and is not particularly limited.

In the above-mentioned production method, the mixing ratio of the polycyclic aromatic carboxylic acid and the allyl alcohol is set so that the COOH group in the polycyclic aromatic carboxylic acid and the OH group in the allyl alcohol are substantially equal. Is preferred.

The polycyclic aromatic carboxylic acid is not particularly limited, but examples thereof include diphenic acid, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, 4,5-phenanthrenecarboxylic acid, and 9,10-anthracene end. Examples thereof include succinic acid, diphthalic acid and anthracenecarboxylic acid. These may be used alone or in combination.

Examples of the above allyl halide include allyl chloride and the like.

Further, an allylphenyl ether compound or an allylphenol compound may be used as a part of the special polycyclic aromatic carboxylic acid allyl ester compound (component B). The above allylphenyl ether compound and allylphenol compound are not particularly limited and can be obtained by a conventionally known production method. For example, the above-mentioned allyl phenyl ether compound is obtained by adding allyl chloride to a phenol resin by a conventional method.

The above-mentioned phenol resin is not particularly limited, but for example, phenol, cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, xylenol, nonylphenol, vinylphenol, isopropylphenol, phenylphenol. , Benzylphenol, chlorphenol, bromophenol, ethoxyphenol, and monovalent phenols such as bisphenol A, bisphenol F, hydroquinone, catechol, resorcinol, etc.
Examples include phenol novolac resins obtained by condensation reaction of aldehyde compounds such as paraformaldehyde and glyoxal by known means, and the above monovalent and divalent phenols. These may be used alone or in combination.

The above specific maleimide compound (component A) and a special polycyclic aromatic carboxylic acid allyl ester compound (B
The ratio of the allyl group in the special polycyclic aromatic carboxylic acid allyl ester compound (component B) is equivalent to one equivalent of the maleimide group in the specific maleimide compound (component A). It is preferable to mix them in the range of 0.1 to 1.5 equivalents. That is, when the compounding ratio of the both is out of the above range, when the semiconductor element is sealed with the obtained resin composition, the crack resistance reliability of the semiconductor device tends to decrease.

One or both of the specific polymaleimide compound (component A) and the special polycyclic aromatic carboxylic acid allyl ester compound (component B) as described above have Si groups and amino groups at the terminals or side chains. It is preferable to use one that has reacted with a silicone compound having at least one of In addition, one or both of an allylphenyl ether compound or an allylphenol compound used in place of a part of the polycyclic aromatic carboxylic acid allyl ester compound (component B) is reacted with the above specific silicone compound. May be used. By using such a modified polymaleimide compound or modified allyl compound alone or in combination, the moisture resistance and the mechanical strength are further improved. The specific silicone compound has a SiH equivalent and an amine equivalent of 10
It is preferable that the Si content is 0 to 15,000 and the Si content is set to 1 to 35% by weight (hereinafter abbreviated as “%”). Further, the amount of the above silicone compound used is as follows:
It is preferable to set it to 40% or less of the total amount of the allylphenyl ether compound, the allylphenol compound and the silicone compound. It is particularly preferable to set it in the range of 3 to 20%. That is, when the amount of the silicone compound used exceeds 40%, the heat resistance and resin strength of the obtained resin composition tend to be significantly reduced.

The curing catalyst (C component) used together with the specific maleimide compound (A component) and the special polycyclic aromatic carboxylic acid allyl ester compound (B component) includes tertiary amines, tertiary amine salts, Examples thereof include basic catalysts such as quaternary ammonium salts and imidazoles.

Examples of the tertiary amines include triethylamine, tri-n-butylamine, tri-n-octylamine, benzyldimethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol,
Triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylguanidine, heptamethylisoguanide, 1,8-diazabicyclo (5,5)
4,0) undecene-7, N, N-dimethylaniline,
N, N, N ', N'-tetramethyldiaminodiphenylmethane, N, N, N', N'-tetramethyl-m-phenylenediamine, N, N, N ', N'-tetramethyl-
Examples thereof include p-phenylenediamine, and examples of the tertiary amine salts include salts of the tertiary amines with triacetate or tribenzoate.

Examples of the quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, trimethylcetylammonium chloride, trimethylcetylammonium bromide, triethylcetylammonium chloride and triethylcetylammonium bromide. Examples of the imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2,4-dimethylimidazole. These curing catalysts may be used alone or in combination of two or more kinds. Then, the compounding amount of the curing catalyst (component C) may be set within the range of 0.2 to 10 parts with respect to 100 parts by weight of the specific polymaleimide compound (component A) (hereinafter abbreviated as “part”). It is preferable from the viewpoint of shortening the curing time. That is, when the compounding amount of the curing catalyst is less than 0.2 part, the catalytic action is small, and further the effect of improving the heat resistance reliability, the humidity resistance reliability and the mechanical strength of the obtained semiconductor device cannot be sufficiently obtained. This is because no further improvement effect can be seen even if the amount is exceeded.

The resin composition used in the present invention may contain a filler, a colorant, a release agent, a flame retardant, a coupling agent such as a silane coupling agent, etc., if necessary, in addition to the components A to C. It can be added appropriately.

As the above-mentioned filler, aluminum oxide,
Magnesium oxide, aluminum hydroxide, aluminum carbonate, diatomaceous earth, calcium silicate, calcined clay, powdered silica, carbon black, kaolin, powdered mica,
Graphite, asbestos, antimony trioxide, glass fiber, rock wool, carbon fiber, etc. The blending amount of the above-mentioned filler is appropriately blended depending on the use, but it can be used up to 500 parts per 100 parts (component A + component B + specific silicone compound in some cases).

As the above colorants, titanium dioxide, yellow lead carbon black, iron black, molybdenum red, ultramarine blue, navy blue,
Examples include cadmium yellow and cadmium red.

Examples of the releasing agent include higher aliphatic paraffins, higher aliphatic esters, natural waxes and synthetic waxes, and examples of the flame retardant include phosphorus compounds.

The resin composition used in the present invention can be manufactured, for example, as follows. That is,
A semi-cured resin composition is obtained by appropriately blending the above-mentioned essential components A to C, a specific silicone compound and, if necessary, the above-mentioned additives, and heating and melting and kneading them in a kneading machine such as a mixing roll machine. To do. The desired resin composition can be obtained by cooling this to room temperature, pulverizing it by a known means, and tableting it as needed. Alternatively, they may be mixed using an appropriate solvent. In this case, one or both of the specific maleimide compound (component A) and the special polycyclic aromatic carboxylic acid allyl ester compound (component B) and the specific silicone compound are melt-mixed in advance prior to the mixing of the above components. You may let it be used.

The encapsulation of the semiconductor element using such a resin composition is not particularly limited and can be performed by a known molding method such as ordinary transfer molding.

The semiconductor device thus obtained is excellent in low stress, heat resistance, and moisture resistance and is highly reliable.

[0037]

As described above, the semiconductor device of the present invention has a specific polymaleimide compound (component A) and a special polycyclic aromatic carboxylic acid allyl ester compound (component B).
And a curing catalyst (component C) are used for resin encapsulation using a special resin composition, and the encapsulation plastic package is different from that of the conventional maleimide resin composition. Is small and has excellent humidity resistance, heat resistance and mechanical strength. Further, in one or both of the polymaleimide compound and the polycyclic aromatic carboxylic acid allyl ester compound in the special resin composition, the reliability is further improved by using a compound that reacts with a specific silicone compound, Higher reliability under severe usage conditions. Further, in the above description, the case where the resin composition in the present invention is applied to the resin encapsulation of the semiconductor element is described. However, the present invention is not limited to this, and the resin composition can be used as an electrical insulating adhesive, a laminate. It is also useful as a board material, a material for forming an insulating layer of a flexible printed circuit board, and a material for manufacturing an insulating film.

Next, examples will be described together with comparative examples.

First, each component shown below was prepared prior to the examples.

[Maleimide resin]

[Chemical 16] Maleimide equivalent: 180

[Allyl ester compound A]

[Chemical 17] Allyl equivalent: 160 [allyl ester compound B]

[Chemical 18] Allyl equivalent: 150

[Allyl phenyl ether compound] An allyl phenyl ether compound having the following structural formula.

[Chemical 19] Allyl equivalent: 280

[Silicone Compound C]

[Chemical 20] Amine equivalent: 2000 [Silicone compound D]

[Chemical 21] Amine equivalent: 2500 [Silicone compound E]

[Chemical formula 22] SiH equivalent: 2000

Then, modified silicone compounds a to d were prepared by blending the above components in the proportions shown in Table 1 below and mixing them by heating.

[0045]

[Table 1]

[0046]

Examples 1 to 8 Next, the above maleimide resin, allyl ester compound, allyl phenyl ether compound, modified silicone compound and the compounds shown in Table 2 below were mixed in the proportions shown in the same table, and mixed with a mixing roll machine ( Temperature 150
K) and kneaded for 3 minutes to prepare a sheet-like material. And
The sheet-shaped material was cooled and pulverized to obtain the desired powdery resin composition.

[0047]

[Table 2]

[0048]

Comparative Examples 1 and 2 No allyl ester compound was used. Otherwise in the same manner as in Example 1, the target powdery resin composition was obtained using the components shown in Table 3 below.

[0049]

[Table 3]

[0050]

[Comparative Examples 3 and 4] A cresol novolak epoxy resin (epoxy equivalent 195) was used in place of the maleimide resin, a phenol novolak resin was used as a curing agent, and the compounds shown in Table 4 below were used in the proportions shown in the table. I was there. A powdery epoxy resin composition was obtained in the same manner as in Example 1 except for the above.

[0051]

[Table 4]

Using the powdery resin compositions obtained in the above Examples and Comparative Examples, semiconductor elements (element size: 9 mm × 9 mm) were molded by transfer molding (molding conditions: pressure 90 kg / cm ² The temperature was 175 ° C. for 2 minutes, and the post-curing step was performed at 200 ° C. for 5 hours to obtain a semiconductor device (size: 20 × 14 × 2 mm) having an 80-pin flat package. The crack resistance and the humidity resistance of the semiconductor device thus obtained were examined. In addition, with respect to a sample obtained by molding only the resin composition by transfer molding (molding condition: temperature 175 ° C. for 2 minutes, post-curing temperature 200 ° C. for 5 hours), cured product characteristics (coefficient of linear expansion, glass transition temperature, bending) The strength and flexural modulus) were measured. The results are shown in Tables 5, 6 and 7 below. The crack resistance test, the moisture resistance reliability test, and the cured product characteristics were measured by the following methods.

[Crack resistance test 1] For each of the 10 semiconductor devices of Examples 1 to 7 and Comparative Examples 1 to 4,
Temperature cycle test from 50 ° C / 5 minutes to 150 ° C / 5 minutes (hereinafter abbreviated as “TCT test”) 1000 times, 200
After repeating 0 times and 3000 times, the number of semiconductor devices having cracks in the package was visually counted.

[Crack resistance test 2] For each of the 100 semiconductor devices of Examples 1 to 7 and Comparative Examples 1 to 4,
After the TCT test of −50 ° C./30 minutes to 150 ° C./30 minutes was repeated 300 times, the number of semiconductor devices having cracks in the package was visually counted.

[Humidity resistance reliability test] For each of the 100 semiconductor devices of Examples 1 to 7 and Comparative Examples 1 to 4, a reliability test for 1000 hours was carried out by a pressure vessel with electric charge application (hereinafter abbreviated as "PCBT test"). ) Was performed and the number of defective products was shown.

[Coefficient of Linear Expansion and Glass Transition Temperature] The above cured product was measured by a thermomechanical analyzer (TMA).

[Flexural Strength and Flexural Modulus] The cured product was measured according to JIS K 6911 at a temperature of 23 ° C. and 260 ° C.

[0058]

[Table 5]

[0059]

[Table 6]

[0060]

[Table 7]

From the results of Table 5, Table 6 and Table 7 above, no cracks were found in the TCT test of the example products, and no defective products were found in the PCBT test results. In addition, regarding the cured product characteristics of the sealing resin, the linear expansion coefficient of the example is lower than that of the comparative example, and the glass transition temperature is high. From this, it is understood that the products of Examples are excellent in low stress resistance, heat resistance and moisture resistance. Further, the examples in which the modified silicone compound is blended have higher bending strength and lower bending elastic modulus than the comparative examples. Therefore, it is understood that the example products are also excellent in mechanical strength.

Claims (3)

[Claims] 1. A semiconductor device obtained by encapsulating a semiconductor element with a resin composition containing the following components (A) to (C). (A) A maleimide compound having two or more maleimide groups in one molecule. (B) At least one polycyclic aromatic carboxylic acid allyl ester compound selected from the group consisting of polycyclic aromatic carboxylic acid allyl ester compounds represented by the following general formulas (1), (2) and (3) .. [Chemical 1] [Chemical 2] [Chemical 3] (C) Curing catalyst. 2. A silicone compound in which at least one of the polymaleimide compound as the component (A) and the polycyclic aromatic carboxylic acid allyl ester compound as the component (B) has at least one of a SiH group and an amino group at the terminal or side chain. The semiconductor device according to claim 1, wherein the semiconductor device reacts with. 3. A resin composition for semiconductor encapsulation containing the following components (A) to (C). (A) A maleimide compound having two or more maleimide groups in one molecule. (B) At least one polycyclic aromatic carboxylic acid allyl ester compound selected from the group consisting of polycyclic aromatic carboxylic acid allyl ester compounds represented by the following general formulas (1), (2) and (3) .. [Chemical 4] [Chemical 5] [Chemical 6] (C) Curing catalyst.