JP2001040183A - Resin paste composition and semiconductor apparatus by use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin paste composition and a semiconductor apparatus by its use for improving peel strength to a support member configured by mainly an organic material, especially the peel strength after absorbing moisture, for improving reflow resistance of a semiconductor apparatus assembled by use thereof without poor wire bonding caused by occurrence of bleed and without problems such as detachment of a sealing material with controlling a lower hygroscopic rate, and further for improving reliability connected to a temperature cycle after practical equipment. SOLUTION: A resin paste composition comprises (A) an epoxy resin or its modified substance, (B) a curing agent reactive to the above described component (A), (C) a glycol ether solvent and (D) a fluoro compound having surface activity. A semiconductor apparatus is constituted by sealing after sticking a semiconductor device to a support member using the resin paste composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for bonding a semiconductor element such as an IC or an LSI to a support member mainly composed of an organic material such as glass / epoxy resin, glass / BT (bismaleimide triazine) resin, or polyimide. And a semiconductor device using the same.

[0002]

2. Description of the Related Art The mounting method of semiconductor devices has shifted from the conventional pin insertion method to the surface mounting method in view of high-density mounting. Further, the structure of the package has been changed to an area terminal type element represented by a name such as BGA (ball grid array) or CSP (chip scale package) due to an increase in the number of pins due to high integration. In the surface mounting method, reflow soldering, which heats the entire board with infrared light or the like, is used for mounting on the board, and the package is heated to a high temperature of 200 ° C or more, so the inside of the package, especially in the adhesive layer or in the sealing material There has been a problem that package cracks occur due to rapid vaporization / expansion of water contained therein, and the reliability of the semiconductor device is reduced. In the area terminal type element, a structure in which a semiconductor element is bonded to a support member mainly composed of an organic material and only one side is sealed is most commonly used. Is made of an organic material having high hygroscopicity and moisture permeability, the die bond layer easily absorbs moisture, and the problem of package cracking due to reflow soldering is particularly serious.

[0003] In particular, 20-
In an area terminal type element using a polyimide film having a thickness of 100 μm as a base material, moisture absorption is more likely to occur, while the base material is easily deformed, so that it easily peels off due to expansion of water and package cracks are extremely likely to occur. There was a problem. As a method for solving this problem, a technique has been used in which the elasticity of the die bond material is increased to make it difficult to deform, thereby suppressing the deformation of the support member and suppressing the separation.

On the other hand, when an area terminal type element using a polyimide film as a base material has a high elastic modulus of a die bonding material, a stress applied to a solder ball due to a temperature cycle after mounting on a wiring board is increased, and connection reliability is increased. There was a problem of the decrease. Furthermore, in the area terminal type element, the wiring density is high, and due to structural problems such as the proximity of the wire bond pad and the die bonding pad or the wiring to the die bond portion, the insulating property to the die bonding material and contamination of the wire bond pad. Is required.
However, no bleeding occurred on the gold plating and the organic substrate, and a die bonding material excellent in reflow resistance was not obtained.

[0005]

SUMMARY OF THE INVENTION The present invention improves the peel strength of a support member composed mainly of an organic material, particularly, the peel strength after moisture absorption, causes poor wire bonding due to bleeding, and peels off a sealing material. There is no problem such as
A resin paste composition and a semiconductor device using the same that can improve the reflow resistance of a semiconductor device assembled using the same by suppressing the moisture absorption rate and improve the connection reliability against a temperature cycle after mounting. To provide.

[0006]

The present invention provides (A) an epoxy resin or a modified product thereof, (B) a curing agent capable of reacting with the component (A), (C) a glycol ether-based solvent, and
(D) The present invention relates to a resin paste composition containing a fluorine compound having surface activity. The present invention also relates to the resin paste composition further containing (E) a filler.

The present invention also relates to a resin paste composition wherein the component (A) is a solid epoxy resin having no fluidity at room temperature (25 ° C.) or a modified product thereof. In the present invention, the component (A) may be contained in an amount of 7 to 95% by weight,
Resin paste composition containing 0.1 to 15% by weight of component, 2 to 30% by weight of component (C), 0.05 to 5% by weight of component (D) and 2 to 90% by weight of component (E) About.

The present invention also relates to the resin paste composition having a viscosity at room temperature (25 ° C.) of 1500 to 8000 poise. The present invention also relates to the resin paste composition, wherein the component (A) is an epoxy resin modified with a butadiene polymer or a butadiene copolymer.

The present invention also relates to a semiconductor device comprising a semiconductor element bonded to a supporting member and sealed using the resin paste composition according to any one of the above. Further, the present invention relates to a semiconductor device in which the support member is mainly composed of an organic material. Further, the present invention relates to a semiconductor device in which the support member mainly composed of the organic material is a member composed mainly of a polyimide film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the epoxy resin (A) used in the present invention or a modified product thereof, the epoxy resin may be a bisphenol A type, a bisphenol F type or a bisphenol AD having two or more epoxy groups in one molecule.
Phenyl glycidyl ether type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin, etc., such as a cresol novolak type, a phenol novolak type and the like. These commercial products include Epicoat 801, 806, 828, 834, 15
2 (both manufactured by Yuka Shell Epoxy Co., Ltd.), Epototo Y
D-128, YDF-8170, YDPN-638P,
YH434 (both manufactured by Toto Kasei Co., Ltd.), FLEP (manufactured by Toray Thiokol Co., Ltd.) and the like can be mentioned.

Examples of the modified epoxy resin include those obtained by modifying the above epoxy resin with a butadiene polymer or a butadiene copolymer, a reaction product with CTBN (carboxy-terminated butadiene nitrile copolymer), dimer acid, and the like. Examples thereof include those modified with rubber. Commercial products of these modified products include YD-172.
(Modified with dimer acid), YR-207 (modified with rubber) (all manufactured by Toto Kasei Co., Ltd.), ACR epoxy R-1309, R-1437-2, R-1206
(Above, manufactured by Asahi Denka Kogyo KK).

In the component (A) used in the present invention,
To suppress bleed, the softening point by the ring and ball method should be 60
-100 ° C, and as a result, it is preferable to use a solid epoxy resin having no fluidity at room temperature (25 ° C). Specifically, the epicoats 1001, 1004,
180H65 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Y
DCN-701S, YDF-2001 (Toto Kasei
DEN438, QUATREX2010 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like.

[0013] Among them, an epoxy resin modified with a butadiene polymer or a butadiene copolymer,
Compatibility between epoxy resin and glycol ether solvent,
It is preferable in terms of adhesive strength after moisture absorption.

The epoxy resin of the component (A) in the present invention is PGE (trade name, manufactured by Nippon Kayaku Co., Ltd.), PP-101.
(Trade name, manufactured by Toto Kasei Co., Ltd.), ED-502, 503,
A reactive diluent having one or more epoxy groups in one molecule such as 509 (trade name, manufactured by Asahi Denka Kogyo KK) can be contained. If the reactive diluent is included in too much, it tends to generate bleed, so when used,
The amount used is preferably 10 parts by weight or less based on 100 parts by weight of the component (A).

[0015] In the resin paste composition of the present invention,
Component (A) is preferably used in an amount of 7 to 95% by weight, more preferably 10 to 90% by weight, based on the total amount of the composition. If the amount exceeds 95% by weight, the adhesiveness at high temperatures tends to decrease, and the reflow resistance tends to decrease. If the amount is less than 7% by weight, the cured paste becomes brittle and the strength tends to decrease.

The component (B), which is a curing agent capable of reacting with the component (A), reacts with the component (A) at a temperature of 150 ° C. or less to suppress the curing temperature at the time of die bonding. It is preferable from the viewpoint of reducing stress. Examples of such a curing agent include a phenol novolak resin, a cresol novolak resin, a xylene copolymer thereof, a dicyandiamide, a hydrazide derivative, a benzoguanamine, a resin having a benzoxazine ring, and a methylhexahydro resin. Acid anhydrides such as phthalic anhydride and methyltetrahydrophthalic anhydride can be used.

Other than the above, phosphoric acid derivatives such as tetraphenylphosphonium / tetraphenylborate, triphenylphosphine / triphenylborane, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-
4-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-dicyanoethoxymethylimidazole,
(B) a curing agent or a curing accelerator such as an imidazole derivative such as an adduct of 2-phenylimidazole-isocyanuric acid;
It can be used as a component.

In the resin paste composition of the present invention,
Component (B) is 0.1 to 15% by weight based on the total amount of the composition.
It is preferably used, more preferably 0.5 to 10% by weight. If this amount exceeds 15% by weight, an unreacted cured product remains, and the properties (such as water absorption) of the paste tend to deteriorate. If this amount is less than 0.1% by weight, the strength of the cured paste decreases and the paste resistance decreases. Reflow properties tend to decrease.

In the present invention, a glycol ether solvent is used as the component (C). By using this, a paste which is excellent in workability and in which bleed is suppressed can be obtained. Here, the glycol ether solvent generally means a solvent in which at least one terminal OH of the glycol forms an ether bond in the form of an alkoxy group or the like. Glycol ether solvents have a boiling point of normal pressure (generally 1
(Atmospheric pressure) of 150 ° C. or higher is preferable because the workability of the paste obtained at a low evaporation rate is excellent, and 250 ° C. or lower is more preferable. As such a glycol ether-based solvent, solvents such as butoxyethanol, butoxyethyl acetate, ethoxyethoxyethanol, butoxyethoxyethanol, and ethoxyethoxyethyl acetate can be used.

In the resin paste composition of the present invention,
The component (C) is preferably contained in an amount of 2 to 30% by weight, more preferably 5 to 20% by weight, based on the total amount of the composition. If the amount is less than 2% by weight, the effect of adding a fluorine compound having surface activity as the component (D) tends to decrease, and bleeding tends to increase. If the amount exceeds 30% by weight, the affinity between the filler and the resin component is poor. Bleeding tends to increase.

As the component (D), a fluorine compound having surface activity is used, and it is preferable that the fluorine compound is soluble in the component (C). By using this, the effect of suppressing bleeding can be improved. Such a fluorine compound generally has a structure in which a fluorine atom is bonded in one molecule but exhibits hydrophobicity (such as a fluoroalkyl group in which some or all hydrogen atoms are substituted with a fluorine atom) and a carboxylic acid. It has a hydrophilic portion such as an acid, sulfonic acid, sulfuric acid, phosphoric acid, amine, ammonium or a salt thereof, a hydroxyl group, or an alkylene glycol chain. For example, a fluoroalkylcarboxylic acid (an alkyl moiety having 2 to 2 carbon atoms)
0), perfluoroalkyl carboxylic acid (alkyl group having 7 to 20 carbon atoms), perfluoroalkyl sulfonic acid salt (alkyl group having 4 to 12 carbon atoms, lithium salt, potassium salt, sodium salt, etc. as salt), perfluoroalkyl Examples thereof include alkylsulfonamidopropyltrimethylammonium salt (alkyl moiety having 6 to 10 carbon atoms) and monoperfluoroalkylethyl phosphate (alkyl moiety having 6 to 16 carbon atoms). Examples of commercially available fluorine compounds include pentadecafluoro-n-octanoic acid, Megafac F-815, R-08 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Can be.

In the resin paste composition of the present invention,
Component (D) is preferably contained in an amount of 0.05 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total amount of the composition. If it is less than 0.05% by weight, the effect of suppressing bleeding tends to decrease, and if it exceeds 5% by weight, the adhesion to the substrate tends to decrease.

In the present invention, a filler (E) is generally used. The (E) filler used is not particularly limited, and various conductive and non-conductive materials are used, but non-conductive materials are preferable in that they maintain insulation between wires under the silicon chip. Non-conductive materials include, for example, silicon nitride, silicon nitride, carbon nitride, aluminum nitride, silicon oxide, aluminum oxide, calcium carbonate, talc,
Insulating inorganic powders such as mica, potassium titanate, diamond powder, and fine powder obtained by subjecting these powders to surface treatment can be used. The shape of the non-conductive filler is not particularly limited, and spherical or acicular, plate-like, or crushed crystalline or amorphous particles can be used.

In the resin paste composition of the present invention,
The amount of the component (E) varies depending on the type within a range that does not impair workability, but is 2 to 90% by weight based on the total amount of the composition.
It is preferably contained, more preferably 20 to 85% by weight. If it is less than 2% by weight, the adhesive strength at the time of heating tends to decrease, and if it exceeds 90% by weight, the viscosity increases and the workability of the resin paste composition tends to decrease.

The resin paste composition according to the present invention may further contain, if necessary, acrylonitrile-butadiene rubber,
Toughness improvers such as styrene-butadiene rubber and urethane acrylate, hygroscopic agents such as calcium oxide and magnesium oxide, silane coupling agents, titanium coupling agents, adhesion enhancers such as acid anhydrides, nonionic surfactants, silicone oils And the like, an ion trapping agent such as an inorganic ion exchanger, a solvent other than the component (C), and the like can be appropriately added.

The viscosity of the resin paste composition according to the present invention is preferably from 1500 to 8000 poise at room temperature (25 ° C.). If it is less than 1500 poise, the paste tends to bleed along the wiring after die bonding, and if it exceeds 8000 poise, discharge becomes difficult and workability tends to be poor.

In order to produce the resin paste composition according to the present invention, each of the components (A) to (E) together with other various additives used as necessary is divided into batches or divided portions and stirred. It can be added to a dispersing / dissolving device such as a bonder, a grinder, a three-roller, or a planetary mixer, and if necessary, heated to mix, dissolve, pulverize, knead or disperse to form a uniform paste. . The dispersing / dissolving devices can be appropriately combined.

In the present invention, a semiconductor device can be obtained by bonding a semiconductor element and a support member using the resin paste composition produced as described above, and then sealing the semiconductor element and the support member. The resin paste composition of the present invention is suitably used for a support member mainly composed of an organic material. Examples of the supporting member mainly composed of an organic material include those mainly composed of an organic material such as glass / epoxy resin, glass / BT resin, and polyimide resin. A supporting member.

In order to adhere a semiconductor element to a support member such as a polyimide film wiring board using the resin paste composition of the present invention, first, the resin paste composition is dispensed on the support member, screen printing method, stamping method and the like. After applying, the semiconductor element is pressure-bonded, and then heat-cured using a heating device such as an oven or a heat block. As the heating temperature at this time, a temperature of 120 to 200 ° C. is generally used. Further, after a wire bonding step, the semiconductor device is sealed by an ordinary method to obtain a completed semiconductor device.

[0030]

Next, the present invention will be described by way of examples. The materials used are as follows. (1) Epoxy resin ・ YDF-170 (trade name, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent 170) ・ PP-101 (trade name, manufactured by Toto Kasei Co., Ltd., alkylphenylglycidyl ether, Epoxy equivalent 230) ・ DEN438 (trade name, manufactured by Dow Chemical Japan Co., Ltd.)
Phenol novolat type epoxy resin, epoxy equivalent
180)

(2) Curing agent H-1 (trade name, phenol novolak resin manufactured by Meiwa Kasei Co., Ltd., OH equivalent: 106) Dicyandiamide (3) Curing accelerator 2PHZ (trade name, Shikoku Chemical Industry Co., Ltd.) TPP-K (trade name, Hokuko Chemical Co., Ltd., organic phosphorus compound)

(4) Butadiene copolymer HaycarCTBN1300X9 (trade name, Ube Industries)
Co., Ltd., carboxy-terminated butadiene acrylonitrile copolymer, carboxyl group equivalent 1500) (5) Solvent-butoxyethanol (boiling point 170 ° C)-ethoxyethoxyethyl acetate (boiling point 217 ° C)

(6) Fluorosurfactant • Pentadecafluoro-n-octanoic acid (7) Filler • Boron nitride powder (manufactured by Mizushima Alloy Iron Co., Ltd.) • Aluminum oxide powder (manufactured by YKK Corporation)

(8) Preparation of Epoxy Resin Modified Solution 25 parts by weight of DEN438, Haycar CTBN
75 parts by weight of 1300X9, 30 parts by weight of ethoxyethoxyethyl acetate and triphenylphosphine
0.3 parts by weight is heated to 110 ° C. and stirring is continued for 2 hours,
A homogeneous butadiene copolymer-modified epoxy resin solution was obtained. (9) Preparation of Curing Agent Solution 50 parts by weight of H-1 and 50 parts by weight of ethoxyethoxyethyl acetate were heated to 110 ° C. and stirred for 1 hour to obtain a uniform phenol resin solution.

Examples 1 and 2 and Comparative Examples 1 and 2 Each material was mixed at the compounding ratios shown in Table 1 and kneaded using a three-roll mill, followed by defoaming at 5 Torr or less for 10 minutes. This was performed to obtain a resin paste composition. The properties (viscosity, peel strength) of this resin paste composition were examined by the following methods. Table 1 shows the results.

(1) Viscosity: The viscosity (Pa · s) at 25 ° C. was measured using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). (2) Peel strength: polyimide wiring board (Hitachi Chemical Industries, Ltd.)
Co., Ltd.) was cut into strips having a width of 5 mm, a resin paste composition was applied thereto, and an 8 mm × 10 mm Si chip (0.4 mm in thickness) was pressed thereon, and then 150 mm in an oven.
The temperature was increased to 30 ° C. in 30 minutes, and cured at 150 ° C. for 1 hour. Place the chip on a heat block and fix it. Fix the end of the film to the end of the spring only and pull it up.
Was measured for the peel strength (g / 5 mm width).

(3) Evaluation of bleed: A resin paste composition obtained by using Examples and Comparative Examples on a wiring using a wiring polyimide wiring substrate having a copper wiring with gold plating and having a wiring width of 0.3 mm and a wiring pitch of 0.5 mm. Was applied at 80 μg / mm ^2, and the silicon chip was die-bonded, cured in a sealed metal dish, and the length of the bleed from the end of the paste was evaluated.
If it is more than 2 mm, the bonding pad is contaminated and cannot be used practically. Curing conditions: temperature rise to 150 ° C in 30 minutes, 150
Cured at ℃ for 1 hour.

(4) Reflow resistance: A polyimide wiring board (manufactured by Hitachi Chemical Co., Ltd.) and a Si chip were cured and bonded under the following curing conditions using the resin paste compositions obtained in Examples and Comparative Examples. . Thereafter, the package was sealed with an epoxy sealing material (CEL-9200, manufactured by Hitachi Chemical Co., Ltd.) to obtain a package for a solder reflow test. The package was allowed to absorb moisture for 48 hours in a thermo-hygrostat set at a temperature and humidity of 85 ° C. and 85%, respectively. Thereafter, solder reflow was performed, and the number of external cracks generated in the package was observed with an ultrasonic microscope. The number of samples in which cracks occurred for five samples is shown. Chip size: 10 mm x 10 mm Package: 24 mm x 24 mm Curing conditions: Heat up to 150 ° C in 30 minutes, cure at 150 ° C for 1 hour.

[0039]

[Table 1]

From the results shown in Table 1, it can be seen that the resin paste compositions of the present invention (Examples 1 and 2) generate much less bleed and have lower reflow resistance than the conventional resin paste compositions (Comparative Example 1). It was excellent.

[0041]

The resin paste composition of the present invention has improved the peel strength with respect to the support member, especially the peel strength after moisture absorption, so that the resin paste composition of the semiconductor device using the support member mainly composed of an organic material can be used. When used as a die bonding material, there is no problem such as defective wire bonding and peeling of a sealing material due to occurrence of bleed on a supporting member (on a gold-plated wiring or an organic material (for example, a polyimide substrate)). As a result, in the semiconductor device of the present invention, the occurrence of reflow crack during solder reflow is reduced, and the reliability is improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/52 H01L 21/52 E (72) Inventor Moritoshi Yoshida 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Works F-term (reference) 4J002 CC032 CD051 CD061 CD111 CD131 CD181 ED027 EF028 EL136 ER016 ER026 EU116 EU186 EV238 EV288 EW048 EW146 EW176 EY016 FD142 FD146 4J036 AA01 AD08 AF06 DC04 DB01 DB01 FA01 FB07 5F047 AA17 BA23 BA34 BA51 BB11

Claims (9)

[Claims] (A) an epoxy resin or a modified product thereof,
A resin paste composition comprising (B) a curing agent capable of reacting with the component (A), (C) a glycol ether-based solvent, and (D) a fluorine compound having surface activity. 2. The method according to claim 1, further comprising (E) a filler.
The resin paste composition as described in the above. 3. The resin paste composition according to claim 1, wherein the component (A) is a solid epoxy resin having no fluidity at room temperature (25 ° C.) or a modified product thereof. 4. Component (A) is 7 to 95% by weight, component (B) is 0.1 to 15% by weight, component (C) is 2 to 30% by weight, and component (D) is 0.05 to 5%. 4. The resin paste composition according to claim 2, comprising 2 to 90% by weight of the component (E). 5. A viscosity at room temperature (25 ° C.) of 1500
The resin paste composition according to any one of claims 1 to 3, wherein the resin paste composition has a viscosity of up to 8000 poise. 6. The resin paste composition according to claim 1, wherein the component (A) is an epoxy resin modified with a butadiene polymer or a butadiene copolymer. 7. A semiconductor device obtained by bonding a semiconductor element to a support member using the resin paste composition according to claim 1 and sealing the semiconductor element. 8. The semiconductor device according to claim 7, wherein the support member is mainly composed of an organic material. 9. The semiconductor device according to claim 8, wherein the support member mainly composed of an organic material is a member mainly composed of a polyimide film.