JP2005314555A - Resin composition and semiconductor device produced by using resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having low stress and high adhesiveness and free from the generation of resin bleeding and provide a semiconductor device having excellent reliability and produced by using the resin composition as a die attach material or a heat-sink attach material for a semiconductor. <P>SOLUTION: The resin composition contains (A) a compound containing a structure expressed by general formula (1) (R<SP>1</SP>is a 3-6C hydrocarbon group; X is -O-, -COO- or -OCOO-; and 1 is an integer of 2-100) in the main chain skeleton and having at least two radically polymerizable carbon-carbon unsaturated bond, (B) a compound containing a structure expressed by general formula (2) (R<SP>2</SP>is a 3-6C hydrocarbon group; Y is -O-, -COO- or -OCOO-; and m is an integer of 5-200) in the main chain skeleton and having at least one functional group expressed by general formula (3) (R<SP>3</SP>is a 1-6C hydrocarbon group; R<SP>4</SP>is a 1-6C hydrocarbon group; and n is an integer of 1-3), and (C) a filler as essential components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a resin composition and a semiconductor device manufactured using the resin composition.

  As part of environmental measures, lead removal from semiconductor products is being promoted, and the lead frame plating is increasingly changed to Ni-Pd for the purpose of deleading from the exterior plating of semiconductor packages. Here, Ni—Pd plating is thinly gold-plated (gold flash) for the purpose of improving the stability of the Pd layer on the surface. Generally, the Ni—Pd plating itself is smooth due to the smoothness of the Ni—Pd plating itself and the presence of gold on the surface. Compared with a silver-plated copper frame or the like, the adhesive strength is reduced. Also, since lead-free solder is used as the solder for mounting on the board, the reflow temperature needs to be higher than in the case of tin-lead solder. Due to an increase in stress due to a decrease in adhesive force and an increase in reflow temperature, the constituent material of the semiconductor package needs to have higher reflow resistance because peeling and cracks are likely to occur in the semiconductor package during reflow. Various measures have been taken with respect to the lead frame to improve the adhesion, but one of them is surface roughening, which is effective in improving the adhesion but is not effective for die attach materials. Resin bleed (resin bleeding) becomes prominent.

On the other hand, the heat sink is usually Ni-plated or Pd-plated, but the surface may be roughened to obtain good adhesion as well. Resin bleed is a serious problem, and large areas are bonded. Since there are many cases where it is necessary to do this, sufficient low stress properties are also required.
As described above, good resin bleedness with respect to the roughened area is required while having sufficiently low stress properties, but the resin compositions that have been used conventionally satisfy these requirements at the same time. There wasn't. (For example, see Patent Document 1)

JP 2003-321508 A

  The present invention relates to a resin composition having a sufficiently low stress even when used for large-area bonding applications, and exhibiting good adhesion and resin bleeding properties, and the resin composition as a die attach material for semiconductors or a heat sink. It is to provide a semiconductor device having excellent reliability by using as an attach material.

Such an object is achieved by the present invention described in the following [1] to [9].
[1] (A) a compound having a structure represented by the general formula (1) in the main chain skeleton and having at least two radical-polymerizable carbon-carbon unsaturated bonds, (B) a main formula having a general formula ( 2. A resin composition comprising the compound represented by 2) and having at least one functional group represented by the general formula (3) and (C) a filler as an essential component.

[2] The resin composition according to item [1], wherein R ^{1 of the} repeating unit represented by the general formula (1) is a tetramethylene group.
[3] The resin composition according to item [1], wherein R ^{1 of the} repeating unit represented by the general formula (1) is a methylethylene group.
[4] The resin composition according to [1], [2] or [3], wherein the compound (A) is di (meth) acrylate.
[5] The resin composition according to [1], [2], [3] or [4], wherein R ^{2 of the} repeating unit represented by the general formula (2) is a methylethylene group.
[6] The resin composition according to [1] [2] [3] [4] or [5], wherein R ³ and R ^{4 in} the general formula (3) are both methyl groups.
[7] The resin composition according to [1], [2], [3], [4], [5], or [6], wherein n in the general formula (3) is 2.
[8] The resin composition according to [1], [2], [3], [4], [5], [6], or [7], wherein the filler is silver powder.
[9] A semiconductor device manufactured using the resin composition according to any one of [1] to [8] as a die attach material or a heat sink attach material.

  According to the present invention, it is possible to provide a resin composition excellent in low-stress property, adhesiveness, and resin bleed property, and a semiconductor device excellent in reliability using the resin composition as a die attach material for a semiconductor or a heat sink attach material. It becomes possible.

R ¹ of the compound (A) having a structure represented by the general formula (1) in the main chain skeleton used in the present invention and at least two carbon-carbon unsaturated bonds capable of radical polymerization is a carbon atom having 3 to 6 carbon atoms. Although it is limited to hydrogen groups, this is not preferred because the resin composition obtained when the carbon number is less than this is too strong and the moisture resistance of the resulting resin composition deteriorates. This is because the intended adhesive strength cannot be obtained because it is too large. R ¹ in the general formula (1) is preferably a tetramethylene group or a methylethylene group among hydrocarbon groups having 3 to 6 carbon atoms. X in the general formula (1) is —O—, —COO—, or —OCOO, and is necessary for imparting flexibility to the cured product. The number of repeating units 1 is limited to an integer of 2 to 100, but this does not exhibit the desired flexibility when the number of repeating units is less than this, and conversely, when it is large, the viscosity becomes too high and the workability is increased. It is because it is not preferable.

In the present invention, a compound (B) having a structure represented by the general formula (2) in the main chain skeleton and having at least one functional group represented by the general formula (3) is used. This is because the compound having the functional group of the general formula (3) is effective in improving the adhesive strength. However, when a commonly used silane coupling agent, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, or 3-aminopropyltrimethoxysilane, is used. Although effective for improving adhesion, resin bleed is likely to occur due to low molecular weight and low surface free energy, especially when used on roughened lead frames, heat sinks, etc. However, it cannot be used practically. Therefore, in the present invention, a compound having a large molecular weight and sufficient compatibility with a curable component used as a base resin in order to suppress the occurrence of resin bleed while having the same adhesive strength improvement as a known silane coupling agent. Use (B). R ^{2 in the} general formula (2) is limited to a hydrocarbon group having 3 to 6 carbon atoms. This is because the resin composition obtained when the carbon number is less than this is too polar. This is because it deteriorates and is not preferable, and when it is more than this, the polarity becomes too low and the desired adhesive strength cannot be obtained, which is not preferable. Y in the general formula (2) is —O—, —COO—, or —OCOO—, and is necessary for imparting flexibility to the cured product. Further, from the viewpoint of compatibility with the base resin, it is particularly preferable that the repeating unit of the general formula (1) is similar to the repeating unit of the general formula (2). The number m of repeating units is limited to an integer of 5 to 200. This is because when the number of repeating units is less than this, the molecular weight is small, so the viscosity is low and resin bleeding tends to occur. This is because excessive workability is not preferable. The functional group represented by the general formula (3) is a functional group used as a normal silane coupling agent, and is not particularly limited, but R ³ and R ⁴ are a methyl group or an ethyl group, and n is 2 or 3. preferable.

Although the compounding quantity of a compound (B) is not necessarily limited, The range of 1-40 weight% is preferable with respect to a compound (A) + (B). If the amount is less than this, the expected effect of improving adhesiveness is not sufficient, and if it is more than this, the viscosity of the resin composition becomes too high, which may cause deterioration in coating workability.
In the present invention, a radical polymerization initiator can be used as necessary. Although it is not particularly limited as long as it is normally used as a thermal radical polymerization initiator, it is desirable that a rapid heating test (decomposition start temperature when a sample is placed on an electric heating plate and heated at 4 ° C./min. In which the decomposition temperature is 40 to 140 ° C. If the decomposition temperature is less than 40 ° C., the preservability of the resin composition at normal temperature is deteriorated, and if it exceeds 140 ° C., the curing time is extremely long, which is not preferable.

  Specific examples of the radical polymerization initiator satisfying this include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3,3,5- Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) Cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (t-butyl) Peroxyvalerate, 2,2-bis (t-butylperoxy) pig 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t- Hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) diisopropylbenzene, t-butylcum Ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m Toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, Di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneo Decanoate, t- Xylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy- 2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropylmono Carbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5- Methyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t -Butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and the like. Two or more types can be mixed and used for control. However, since the present invention is usually used under illumination such as a fluorescent lamp, when a photoinitiator is contained, an increase in viscosity is observed due to a reaction during use, and therefore it cannot be blended. Further, various polymerization inhibitors and antioxidants may be added in advance in order to improve the storage stability of the resin composition.

As the filler (C) used in the present invention, silver powder is usually used, and preferably 70% by weight or more in the resin composition, but gold powder, aluminum nitride, boron nitride, silica, alumina and the like can also be used. . If necessary, additives such as a reactive diluent, an antifoaming agent, a surfactant, and an epoxy resin can be added to the resin composition of the present invention.
The resin composition of the present invention can be produced, for example, by premixing each component, kneading using three rolls, and degassing under vacuum.
A known method can be used as a method of manufacturing a semiconductor device using the resin composition of the present invention.

[Examples 1 and 2]
As the component (A), Blemmer PDP-400 (manufactured by NOF Corporation, the repeating unit (R ¹ X) in the general formula (1) is propylene oxide, the repetition number 1 is about 9, hereinafter, PDP-400), Blemmer PDT-800 (manufactured by NOF Corporation, the repeating unit (R ¹ X) in the general formula (1) is tetramethylene oxide, the repeating number 1 is about 5, hereinafter referred to as PDT-800), and the component (B) Silyl SAT030 (Kanebuchi Chemical Industry Co., Ltd.), repeating unit (R ² Y) in general formula (2) is propylene oxide, terminal is dimethoxysilane, molecular weight of about 5000, hereinafter SAT030), average particle as component (C) A flaky silver powder (hereinafter referred to as silver powder) having a diameter of 3 μm and a maximum particle diameter of 20 μm was used. Component (A), Component (B), Component (C), Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, decomposition temperature in rapid heating test: 126 ° C., hereinafter initiator), and lauryl acrylate (Kyoeisha) Chemical Co., Ltd., light ester LA, hereinafter LA) was blended as shown in Table 1, kneaded using three rolls, and defoamed to obtain a resin composition. The blending ratio is parts by weight.

[Example 3]
As the component (B) to be used, Silyl SAT200 (Kanebuchi Chemical Industry Co., Ltd., repeating unit (R ² Y) in the general formula (2) is propylene oxide, terminal is dimethoxysilane, molecular weight is about 9000, hereinafter SAT200). A resin composition was prepared in the same manner as in Example 1 except that it was used.

[Comparative Examples 1 and 2]
The resin composition was obtained in the same manner as in Example 1 by blending at the ratio shown in Table 1.
[Comparative Example 3]
Resin composition as in Example 1 except that KBM-403E (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, hereinafter referred to as KBM-403E) is used instead of the component (B) used. It was created.
The obtained resin composition (die attach paste) was evaluated by the following methods. The evaluation results are shown in Table 1.

Evaluation Method / Viscosity: Using an E-type viscometer (3 ° cone), the value at 25 ° C. and 2.5 rpm was measured immediately after the production of the die attach paste. The viscosity immediately after production is 15 to 25 Pa.s. The case in the range of s was regarded as acceptable. The unit of viscosity increase rate is%.
Resin bleed: 10 points dispensed on a gold-flashed Ni-Pd frame using a 22G (inner diameter 0.47 mm) nozzle and cured in a 150 ° C. oven for 15 minutes. The length of the resin bleed after curing was measured with a microscope, and the maximum value obtained by dispensing 10 points was defined as the resin bleed length. 50 μm or less was accepted. The unit is μm.
Adhesive strength: Using a paste, a 6 × 6 mm silicon chip was mounted on a gold-flashed Ni-Pd frame and cured in an oven at 150 ° C. for 15 minutes. After curing, the die shear strength during heating at 260 ° C. was measured using an automatic adhesive force measuring device. The case where the die shear strength when heated at 260 ° C. was 30 N / chip or more was regarded as acceptable. The unit of adhesive strength is N / chip.
Chip warpage: A 6 × 6 mm silicon chip was mounted on a gold-flashed Ni—Pd frame and cured in a 150 ° C. oven for 15 minutes. The amount of warpage of the chip surface after curing was measured with a surface roughness meter. 40 μm or less was accepted. The unit is μm.

  Since the resin composition of the present invention is excellent in low stress property and adhesiveness and exhibits good resin bleed properties, the present invention can be used as a die attach material or a heat sink attach material, thereby providing an unprecedented highly reliable semiconductor. Packages can be provided.

Claims (9)

(A) A compound having a structure represented by the general formula (1) in the main chain skeleton and having at least two radical-polymerizable carbon-carbon unsaturated bonds, (B) a main chain skeleton represented by the general formula (2) A resin composition comprising the structure shown and having at least one functional group represented by general formula (3) and (C) a filler as an essential component.

The resin composition according to claim ¹ , wherein R ^{1 of the} repeating unit represented by the general formula (1) is a tetramethylene group. The resin composition according to claim ¹ , wherein R ^{1 of the} repeating unit represented by the general formula (1) is a methylethylene group. The resin composition according to claim 1, 2 or 3, wherein the compound (A) is di (meth) acrylate. The resin composition according to claim 1, 2, 3 or 4, wherein R ^{2 of the} repeating unit represented by the general formula (2) is a methylethylene group. 6. The resin composition according to claim 1, wherein R ³ and R ^{4 in} the general formula (3) are both methyl groups. 7. The resin composition according to claim 1, wherein n in the general formula (3) is 2. The resin composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the filler is silver powder. A semiconductor device manufactured using the resin composition according to claim 1 as a die attach material or a heat sink attach material.