JPH11124487A - Cyanic acid ester-maleimide liquid resin composition and sealed semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealed semiconductor element having high reliability. SOLUTION: This cyanic acid ester-maleimide liquid resin composition is obtained by mixing 100 pts.wt. of a resin composition comprising (A) 25-60 pts.wt. of a cyanic acid ester-maleimide resin, (B) 35-70 pts.wt. of an epoxy resin which is a liquid form at ambient temperature and (C) 0.1-5 pts.wt. of an epoxy group-containing silicone oil premixed with a cyanic acid ester resin with (D) 0.1-5 pts.wt. of a curing catalyst comprising a metallic chelate or a metallic salt and (E) 100-900 pts.wt. of a filter. The sealed semiconductor device is sealed with the cyanic acid ester-maleimide liquid resin composition. Thereby, the sealed semiconductor device, sealing a semiconductor element therein, excellent in adhesion and electrical characteristics, hardly causing voids or warpage of chips and remarkably improved in characteristics such as reliability of moisture resistance after soldering can be provided by using the cyanic acid ester- maleimide liquid resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid sealing resin composition for sealing semiconductor elements in PGA (pin grid array), BGA (ball grid array), MCM (multi-chip module) and FC (flip chip). The present invention relates to a semiconductor device using the composition.

[0002]

2. Description of the Related Art For resin sealing of electronic parts and semiconductor elements,
Epoxy resin, silicone resin, polybutadiene, polyurethane, phenol resin and the like are used depending on the use and purpose. Among them, epoxy resins are most widely used in terms of mechanical properties, electrical properties, heat resistance, adhesiveness, chemical resistance and the like. Particularly, a large amount of epoxy resin is used as a molding compound for encapsulating semiconductor elements.

[0003] With the recent trend toward thinner and smaller electronic components and the increase in the degree of integration, the shape of semiconductor devices has been diversified, and conventional epoxy resin molding compounds have been applied to all types of semiconductor devices. It has become difficult to respond. In particular, in the case of a highly integrated semiconductor element, in which the spacing between bonding wires must be reduced, the bonding wire may bend due to the pressure of the resin flowing in at the time of molding, and may be in contact with an adjacent bonding wire. Can be. In such recent miniaturized and highly integrated semiconductor devices, a liquid resin at room temperature, which does not apply excessive pressure to the bonding wires during resin sealing, is advantageous.

In order to improve the reliability of the BGA or MCM package, it is essential that the sealing material and the semiconductor element or the substrate resist have high adhesion. However, since the molding compound is molded using a mold, a mold release agent is required, and there is a limit in improving the adhesion. Since the liquid sealing resin that does not use a mold for molding does not use a release agent as an essential component, it can obtain much better adhesion than a molding compound and can also improve its reliability. In addition, in the case of a semiconductor device in which a semiconductor element is connected to an external electrode with a solder ball instead of a bonding wire, a gap of 20 to 200 μm between the semiconductor element and the packaging substrate is sealed with a resin using a capillary phenomenon. Implementation is difficult unless the resin is liquid at room temperature.

[0005] Liquid epoxy resin compositions have been proposed as liquid sealing resins to meet these demands. However, when the liquid sealing resin is an epoxy resin composition, an amine compound, an acid anhydride, a phenol compound, or the like is essential as a curing agent. Therefore, these epoxy liquid sealing resins have insufficient heat resistance or moisture resistance. For this reason, there is a problem that the semiconductor sealing device cannot obtain sufficient reliability, and improvement of the reliability of the liquid sealing agent is strongly desired.

Further, the material for fixing the semiconductor element has been expanded from lead frames and ceramics to inexpensive and easily processed organic substrates. In particular, a thin organic substrate is likely to be warped during resin sealing, and a liquid sealing resin that does not cause the warpage is desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object to provide a cyanate ester-maleimide having excellent adhesion, heat resistance, moisture resistance and electric properties. An object of the present invention is to provide a semiconductor sealing device in which a semiconductor element is sealed with a liquid resin composition and a cured product of the cyanate-maleimide liquid resin composition.

[0008]

DISCLOSURE OF THE INVENTION The present invention is based on a study of a liquid resin composition for sealing a semiconductor element using a cyanate-maleimide resin (hereinafter referred to as "BT resin") and an epoxy compound. Select an epoxy resin or epoxy resin mixture that is liquid at room temperature, without using any epoxy curing agents or curing accelerators such as ordinary amine resins or compounds, acid anhydrides, phenolic resins, etc. When the epoxy group-containing silicone oil and epoxy resin pre-mixed in the resin are cured by reacting with a specific curing catalyst, a resin having excellent heat resistance, moisture resistance, and adhesion required for a semiconductor element encapsulation resin is obtained. It was found that warping was sufficiently small even when sealing was performed on a thin fiber-reinforced resin substrate, and this was further studied. The present invention has been completed.

That is, the present invention relates to (A).
Resin composition 100 comprising 60 parts by weight, (B) 35 to 70 parts by weight of an epoxy resin which is liquid at room temperature, and (C) 0.1 to 5 parts by weight of an epoxy group-containing silicone oil premixed with BT resin.
BT resin liquid resin composition comprising (D) 0.1 to 5 parts by weight of a curing catalyst comprising a metal chelate or a metal salt and (E) 200 to 900 parts by weight of a filler, and the BT resin. A semiconductor device characterized by being sealed using a liquid resin composition.

Hereinafter, each component constituting the composition of the present invention will be described in detail. First, the BT resin of the component (A) of the composition of the present invention is obtained by weighting a monomer of a polyfunctional cyanate ester or a prepolymer of the cyanate ester and a monomer of a polyfunctional maleimide or a prepolymer of the maleimide. Pre-reacted or pre-mixed at a ratio of 95: 5 to 5:95. The component (A) imparts important properties to the composition, such as heat resistance, moisture resistance and adhesion.

Usually, commercially available polyfunctional cyanate esters include 2,2-bis (4-cyanatophenyl) propane, and polyfunctional maleimides include 2,2-bis (4- There is N-maleimidophenyl) methane, which can be suitably used. The polyfunctional cyanate ester and the polyfunctional maleimide are not limited to the above. Also,
The BT resin of the component (A) preferably has a melt viscosity at 100 ° C. of 0.1 to 1.0 poise.

The liquid epoxy resin as the component (B) may be liquid at room temperature, and may be a single epoxy resin or a mixture of two or more epoxy resins. Specific epoxy resins include diglycidyl ethers of 2,2-bis (4-hydroxyphenyl) propane, butadiene diepoxide, vinylcyclohexene dioxide, bifunctional epoxy compounds such as diglycidyl ether of resorcinol, polyhydric phenol or Glycidyl ether and polyglycidyl ester obtained by condensing polyhydric alcohol and epichlorohydrin, novolak epoxy resin obtained by condensing novolak-type phenolic resin and epichlorohydrin, epoxidized polyolefin epoxidized by peroxide method, epoxidized polybutadiene And a pre-reaction is appropriately used as a mixture of two or more so as to be liquid at room temperature.

A monoepoxy compound can be used in combination as appropriate. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether and octylene oxide. , Dodecene oxide and the like. The component (B) reduces the viscosity of the composition and improves workability without lowering the heat resistance and moisture resistance of the component (A).

The epoxy group-containing silicone oil premixed with the component (C) BT resin is represented by the following general formula (1). General formula (1): R ¹ Si (R) ₂ -O- (SiRR ² -O) _n -Si (R) ₂ R ¹ (where n is an integer of 1 to 300, and R is a methyl group or A phenyl group; R ¹ and R ² represent an organic group having a methyl group, a phenyl group or an epoxy group, and 1 to 10 of R ¹ or R ² represent an organic group having an epoxy group.) Epoxy The group-containing silicone oil can be used alone or as a mixture, and the compounding amount is 0.1 to 5 parts by weight in the total of 100 parts by weight of the components (A), (B) and (C) of the present invention. Used in

For the preparation of the composition of the present invention, the epoxy group-containing silicone oil is preliminarily mixed with part or all of the component (A) or with the same type thereof. When all the components of the present invention are mixed at the same time, when they are added, a part of the silicone oil bleeds, and the properties such as adhesive strength of the obtained composition deteriorate. The pre-mixing is performed by adding and mixing 30% by weight or less of the present epoxy group-containing silicone oil to the molten BT resin. If the amount exceeds 30% by weight, phase separation tends to occur, which is not preferable. Specific mixing conditions are, for example, 2,2-bis (4-cyanatophenyl)
In the case of a resin consisting of 95 parts by weight of propane and 5 parts by weight of 2,2-bis (4-N-maleimidophenyl) methane, the temperature is 140 to 180.
Stir and mix at 4 ° C for 4-18 hours. This (C) component is
This has the effect of reducing the warpage of the BGA and MCM package substrates.

As the component (D), a metal chelate or metal salt is used as a curing catalyst. Metal chelate is JP-B-49-168
No. 00 is disclosed as a method for producing polycyanurate,
It is known to be a catalyst for the sole curing of cyanate esters. It is known from JP-B-61-501094 that a metal salt of a carboxylic acid serves as a catalyst for curing a cyanate ester alone. All of them are excellent catalysts for curing the BT resin and epoxy of the present invention.

Specifically, generally, 1 is used as a metal chelate.
Non-ionic or ionic metal chelates having up to 6 or more chelating rings, with iron, cobalt, zinc, tin, copper, manganese, zirconium, titanium, vanadin, aluminum and magnesium being preferred. The ligand of the metal chelate is known in the art and is not particularly limited, but acetylacetone, salicylaldehyde, benzoylacetone, and the like, which are easily available, are preferable. The metal as the metal salt catalyst of the carboxylic acid is preferably iron, cobalt, zinc, tin, copper, manganese, zirconium, titanium, vanadin, aluminum and magnesium, and the carboxylic acid is preferably naphthenic acid or octylic acid.

The amount used as a catalyst varies depending on the type of the catalyst, but is determined by considering both the sufficient storage life and the required curing rate, and is usually (A), (B) or (B).
(C) 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight based on 100 parts by weight of the total of the components. The metal chelate or metal salt catalyst described in the present invention is composed of 1
A mixture of two or more species may be used, and the composition of the present invention exhibits properties such as heat resistance and moisture resistance.

The filler as the component (E) may be a known one in this type of composition, and may be an inorganic or organic fine powder, fibrous material or the like. For example, synthetic or natural silica powder, fused silica powder, mica, alumina, bauxide, titanium oxide, calcium carbonate, antimony trioxide, silicon nitride, silicon carbide, boron nitride, barium sulfate, clay, talc, carbon black, graphite, etc. Inorganic powder, synthetic resin powder, river sand, slate powder, glass fiber, rock wool, synthetic fiber, etc., and these may be used alone or in combination of two or more. However, the filler is preferably dried before use to reduce the water content to 0.3% or less, and a silane coupling agent or other material is used to improve the adhesion to the resin component which is a main component of the present invention. It is preferable to use it in combination with a processing aid. In addition,
The amount of this filler varies depending on its type and viscosity.
100 parts by weight of the total of components (A), (B) and (C)
Up to 900 parts by weight.

The appearance and shape may be adjusted by adding a necessary amount of a coloring agent, an antifoaming agent, a leveling agent, a surfactant and the like to the liquid resin composition of the present invention. The liquid resin composition of the present invention can be obtained by uniformly kneading the necessary components using a mixing device such as a grinder, a roll, or a kneader. There is no particular limitation on the specific method such as the mixing order.

[0021]

EXAMPLES Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by these examples. The description of “parts” and “%” in Examples and the like is based on weight unless otherwise specified. Example 1 1,795.5 parts of 2,2-bis (4-cyanetophenyl) propane,
94.5 parts of bis (4-N-maleimidophenyl) methane and epoxy group-containing silicone oil (Product name: BY16-855, Toray
Dow Corning Silicone Co., Ltd., epoxy equivalent 65
0, in which R ¹ is a glycidyl group and R and R ² are methyl groups in the general formula (1). 210 parts are stirred and mixed at 170 ° C. for 5 hours, and premixed with 10% of an epoxy group-containing silicone oil. (Hereinafter referred to as “preliminary mixture C1”).

BT resin (2,2-bis (4-cyanetophenyl) propane / bis (4-N-maleimidophenyl) methane = 95/5, viscosity 0.10 poise, 100 ° C., Mitsubishi Gas Chemical Co., Ltd.
Made; BT2100B) 15 parts, bisphenol F type epoxy resin
(Product name: EPICLON 830 LVP, Dainippon Ink and Chemicals, Inc.)
Resin composition consisting of 55 parts of neopentyl glycol diglycidyl ether and 15 parts of premix C1
(A: B: C = 28.5: 70: 1.5), 1.0 part of iron acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing catalyst, and γ-glycidoxypropyltrimethoxysilane as a coupling agent
(Product name: A-187, manufactured by Nippon Unicar Co., Ltd.) 2 parts, average particle size
400 parts of 10 μm spherical silica and 0.5 parts of carbon black as a colorant (product name: MA-100 (manufactured by Mitsubishi Chemical Corporation)) are mixed for 1 hour with an Ishikawa Kakuhan Raikai machine, defoamed, and BT resin liquid A resin composition (hereinafter, referred to as “composition A”) was obtained.

Example 2 10 parts of BT2100B, 35 parts of EPICLON 830 LVP, polypropylene glycol diglycidyl ether (trade name: PG-207S,
A resin composition consisting of 30 parts of Toto Kasei Co., Ltd.) and 125 parts of a premix C125 (1.5 parts of aluminum acetylacetone aluminum (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing catalyst, A-187 2
Parts, 450 parts of spherical silica having an average particle size of 10 μm and MA-100
Mix 0.5 part with Ishikawa Kakuhan Raikai machine for 1 hour,
Degas and remove the BT resin liquid resin composition (hereinafter referred to as "Composition B").
).

Example 3 BT resin (2,2-bis (4-cyanetophenyl) propane /
Bis (4-N-maleimidophenyl) methane = 90/10, viscosity
0.10 poise, 100 ° C, manufactured by Mitsubishi Gas Chemical Co., Ltd .; BT2100) 17
Parts, EPICLON 830 LVP 43 parts, neopentyl glycol diglycidyl ether 12 parts, epoxidized polybutadiene (product name: E1000-3.5, manufactured by Nippon Petrochemical Co., Ltd.) 3 parts and premixed product C1 25 parts , Zinc octylate 2.0 parts, A-187 1 part, 450 parts of spherical silica having an average particle diameter of 10 μm and 0.5 part of MA-100 were mixed for 1 hour with an Ishikawa-type kakuhan raikai machine, defoamed, and BT resin liquid A resin composition (hereinafter, referred to as “composition C”) was obtained.

Example 4 1,615 parts of 2,2-bis (4-cyanetophenyl) propane, 85 parts of bis (4-N-maleimidophenyl) methane and an epoxy-containing silicone oil (product name: SF 8411, Dow Corning Toray) -Silicone Co., Ltd., epoxy equivalent 3,000, in the general formula (1), 1 to 10 of R ² is a glycidyl group,
R and R ¹ correspond to methyl groups) 300 parts were stirred and mixed at 170 ° C. for 4 hours to obtain a pre-mixed product containing 15% of an epoxy group-containing silicone oil (hereinafter referred to as “pre-mixed product C2”). . 20 parts of BT2100, 40 parts of EPICLON 830 LVP, 20 parts of aliphatic cyclic epoxy resin (product name; Celloxide 2021, manufactured by Daicel Chemical Industries, Ltd.), and 20 parts of premix C2, 1.5 parts of zinc octylate, A-187 1 Parts, 400 parts of spherical silica having an average particle size of 10 μm and 0.5 parts of MA-100 were mixed for 1 hour with an Ishikawa-type kakuhan raikai machine, defoamed, and BT resin liquid resin composition (hereinafter referred to as “composition D”). ).

Comparative Example 1 32 parts of EPICLON 830 LVP, 47 parts of methyltetrahydrophthalic anhydride as a curing agent for epoxy resin, celoxide
2021 11 parts, E1000-3.5 3 parts, 2-ethyl-4-methylimidazole 0.5 parts, A-187 2 parts, 450 parts of spherical silica having an average particle diameter of 10 μm and 0.5 parts of MA-100 were supplied to Ishikawa Kakuhanraikai Machine Co., Ltd. For 1 hour and defoamed to obtain an epoxy liquid resin composition (hereinafter, referred to as “composition E”).

Comparative Example 2 30 parts of BT2100, 55 parts of EPICLON 830 LVP, 15 parts of neopentyl glycol diglycidyl ether, 1.0 part of iron acetylacetone, 2 parts of A-187, spherical silica having an average particle diameter of 10 μm
400 parts and 0.5 part of MA-100 were mixed in an Ishikawa kakuhan raikai machine for 1 hour and defoamed to obtain a BT resin liquid resin composition (hereinafter, referred to as “composition F”). Comparative Example 3 BT2100 28 parts, EPICLON 830 LVP 55 parts, neopentyl glycol diglycidyl ether 15 parts, epoxy group-containing silicone oil (BY16-855) 2 parts, iron acetylacetone
1.0 part, A-187 2 parts, Spherical silica 400 with average particle size of 10 μm
Part and MA-1000.5 part were mixed for 1 hour using an Ishikawa kakuhan raikai machine and defoamed to obtain a BT resin liquid resin composition (hereinafter, referred to as “composition G”).

Using the compositions obtained in Examples and Comparative Examples, a glass cloth-based copper-clad laminate CCL-
The board of HL830 (Mitsubishi Gas Chemical Co., Ltd.)
Attach a 3 mm wide frame, seal the silicon chip inside the frame,
After heating at 110 ° C. for 3 hours, it was cured by heating at 160 ° C. for 3 hours to obtain a test piece. The test results are shown in Table 1. A remarkable effect of the present invention was observed.

[0029]

[Table 1] Test items Unit Examples Comparative examples, etc. 1 2 3 4 1 2 3 Composition name (sign) ABCD F G Viscosity (poise) 1300 1300 1400 1300 650 1300 1300 Glass transition temperature (° C) 172 175 171 178 158 158 175 175 Flexural strength (kg / mm ² ) 13 14 15 16 14 14 14 Volume resistivity (× 10 ¹⁰ Ω cm) 9 9 8 9 0.2 9 9 Adhesion (kg / cm) 0.30 0.30 0.32 0.30 0.10 0.21 0.15 Warpage (μm) 110 100 100 100 120 120 110 Water absorption (%) 0.86 0.85 0.82 0.89 0.95 0.87 0.86 Soldering heat resistance 0/30 0/30 0/30 0/30 18/30 6/30 10 / 30

The measurement of various performances was performed as follows.・ Viscosity: Unit poise, 25 of the obtained liquid resin composition
C. Viscosity was measured using a B-type viscometer.・ Glass transition point: unit ° C, the obtained liquid resin composition is cast into a mold, heated at 110 ° C for 3 hours, and cured at 160 ° C for 3 hours to prepare a 2 × 6 × 50 mm test piece. Was measured using a thermomechanical analyzer.・ Bending strength: Unit: kg / mm ² , test specimen similar to glass transition temperature, measured using an autograph. -Moisture absorption: Unit%, make a test piece similar to the case of glass transition temperature, treat this test piece under PCT condition of 121 ° C, 2 atm, 100% relative humidity for 24 hours, and measure the rate of weight increase after the treatment. The moisture absorption was calculated.

Amount of warpage: Unit μm, using a liquid resin composition, sealing and heating the above-mentioned test piece. It measured using.・ Adhesion: Unit: kg / cm, Adhere a 5 cm × 10 cm flow-stop frame to the glossy side of the electrolytic copper foil with a thickness of 35 μm, inject the obtained liquid resin composition into the frame, and keep it at 110 ° C for 3 hours. After heating,
A test piece was prepared by curing at 160 ° C. for 3 hours, and the peel strength on the glossy side of the electrolytic copper foil having a width of 10 mm was measured using an autograph.

Solder heat resistance: 30 pieces of the above test pieces obtained by sealing and heating using the liquid resin composition were subjected to a moisture absorption treatment at 85 ° C., 85% for 24 hours. Thereafter, it was immersed in a solder bath at 240 ° C. for 1 minute. afterwards,
The surface of the package and the cross section were observed with a stereoscopic microscope, and the results of evaluating the occurrence of external resin cracks and the presence or absence of internal cracks or peeling were shown as the number of defects / number of tests.・ Volume resistivity: Unit: Ωcm, the obtained liquid resin composition was cast into a mold, heated at 110 ° C. for 3 hours, and then cured at 160 ° C. for 3 hours to prepare a test piece having a thickness of 2 mm and a diameter of 90 mm. This test piece was subjected to PCT conditions of 121 ° C, 2 atm and 100% relative humidity.
After treatment for 24 hours, measurement was performed using an insulation measuring device.

[0033]

As apparent from the detailed description of the invention and the following, Examples, Comparative Examples and Table 1, the BT resin liquid resin composition of the present invention has a high glass transition temperature,
The semiconductor sealing device using the BT resin liquid resin composition of the present invention is excellent in electrical characteristics, moisture resistance and solder heat resistance, has a small amount of warpage, and is highly reliable and useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 73/06

Claims (2)

[Claims] (A). Cyanate-maleimide resin
25-60 parts by weight, (B) .Epoxy resin 35 ~ which is liquid at room temperature
70 parts by weight and (C) epoxy group-containing silicone oil premixed with cyanate-maleimide resin 0.1 to 5
To 100 parts by weight of the resin composition consisting of parts by weight, (D) 0.1 to 5 parts by weight of a curing catalyst comprising a metal chelate or metal salt and
(E) A cyanate-maleimide liquid resin composition obtained by mixing 100 to 900 parts by weight of a filler. 2. A semiconductor device which is encapsulated with the cyanate-maleimide liquid resin composition according to claim 1.