JP2012236873A - Resin paste composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin paste composition excellent in adhesiveness to gold and silver, and to provide a semiconductor device.SOLUTION: This resin paste composition includes: (A1) an acryloyloxy group-containing compound having two acryloyloxy groups, and a 5-20C alicyclic structure or 4-20C aliphatic structure in one molecule; (A2) a methacryloyloxy group-containing compound having two methacryloyloxy groups, and a 5-20C alicyclic structure or 4-20C aliphatic structure in one molecule; (B) a polymerization initiator; and (C) a filler. The semiconductor device includes: a supporting member; a semiconductor element put on the surface of the supporting member; a cured product of the resin paste composition intervening between the surface of the supporting member and the semiconductor element so as to fix the supporting member and the semiconductor element; and a sealing material for sealing a part of the supporting member and the semiconductor element.

Description

The present invention relates to a resin paste composition suitable for bonding a semiconductor element such as an IC or LSI to a lead frame, a glass epoxy wiring board or the like, and a semiconductor device using the same.

  Generally, in a semiconductor device, an element such as a semiconductor chip is fixed to a die pad portion (pedestal) of a lead frame with a die bonding material, and further, these elements and a portion of the lead frame other than the external connection portion are sealed with a sealing material. It has a stopped structure. Conventionally, gold-silicon eutectic, solder, resin paste composition, and the like are known as the die bonding material, but resin paste compositions are widely used in terms of workability and cost.

  The mounting method of this semiconductor device is a conventional pin insertion mounting method (from the point of high density mounting) (the lead terminal of the semiconductor device is passed through a hole (through hole) of a substrate made of a printed wiring board etc. and soldered on one or both sides) To a surface mounting method (a method in which a semiconductor device is mounted on a solder-printed substrate and this solder is heated and melted with infrared rays to fix the semiconductor device to the substrate). In this surface mounting method, reflow soldering is used to heat the entire substrate with infrared rays or the like in a state where the semiconductor device is mounted on the substrate as described above, and the package is heated to a high temperature of 200 ° C. or higher, so that moisture is absorbed. The paste layer may peel off due to rapid expansion of moisture. For this reason, the die bonding paste is required to have a high die shear bonding strength between the semiconductor element (silicon chip and the like) and the lead frame (hereinafter also referred to as bonding strength).

  In this regard, Patent Document 1 discloses an acrylic ester compound or a methacrylic ester compound, a radical initiator, an epoxy resin, an epoxy resin curing agent, for the purpose of improving the adhesive strength of the resin paste composition to the copper lead frame, and the like. And a resin paste composition containing silver powder is disclosed.

JP 2002-179769 A

Various supporting members (such as lead frames) for semiconductor elements are used in addition to the copper frame. For example, a lead frame in which the surface of copper or the like is silver-plated or a lead frame in which two layers of nickel / gold are plated is also used. In recent years, a lead frame called Pre Plating Lead Frame (hereinafter abbreviated as PPF) in which a lead frame is plated with three layers of nickel / palladium / gold has been increasing. Then, it is desired to firmly bond the semiconductor element to the die pad portion of the lead frame having silver or gold on the surface.
The present invention particularly relates to a resin paste composition that can favorably adhere a semiconductor element to the surface of a support member made of gold or silver, and to adhere a semiconductor element and a support member by using this resin paste composition. It is an object of the present invention to provide a semiconductor device.

  The inventors of the present invention provide a support in which a resin paste composition containing both a specific acryloyloxy group-containing compound and a specific methacryloyloxy group-containing compound has a surface made of gold or silver due to the synergistic effect of these two compounds. The present inventors have found that a semiconductor element can be satisfactorily bonded to a member and completed the present invention.

That is, the present invention provides the following.
(A1) An acryloyloxy group-containing compound having two acryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms in one molecule, (A2) 1 molecule A methacryloyloxy group-containing compound having two methacryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms, (B) a polymerization initiator, and (C ) A resin paste composition containing a filler.
Hardened material of the resin paste composition for fixing the support member and the semiconductor element by interposing between the support member, the semiconductor element installed on the surface of the support member, and the surface of the support member and the semiconductor element And a semiconductor device having a sealing material for sealing a part of the support member and the semiconductor element.

  According to the resin paste composition and the semiconductor device of the present invention, the semiconductor element can be satisfactorily bonded to the support member whose surface is made of gold or silver.

It is a top view explaining the measuring method of volume resistivity.

[Resin paste composition]
The resin paste composition of the present invention is (A1) acryloyloxy having two acryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms in one molecule. Group-containing compound, (A2) a methacryloyloxy group-containing compound having two methacryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms in one molecule; B) contains a polymerization initiator and (C) a filler.

<(A1) Acryloyloxy group-containing compound>
In the resin paste composition of the present invention, the (A1) acryloyloxy group-containing compound (hereinafter sometimes referred to as “component (A1)”) is an essential component. The resin paste composition not containing this (A1) acryloyloxy group-containing compound has insufficient adhesive strength between the gold or silver surface and the silicon surface of the semiconductor element.

The (A1) acryloyl group-containing compound used in the present invention is a component that can be said to be a matrix in which the filler (C) described later is dispersed, like the (A2) methacryloyl group-containing compound described later, and is preferably a curable ( A1) As the acryloyl group-containing compound, an acrylate compound can be used.
The (A1) acryloyloxy group-containing compound used in the present invention includes two acryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms in one molecule. If it has, there is no restriction in particular, for example, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1, Examples thereof include tricycloalkane group-containing diacrylate compounds such as 10-decanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, and tricyclodecane dimethanol diacrylate.

  5-15 mass% is preferable and, as for content of (A1) component in a resin paste composition, 6-12 mass% is especially preferable. When the content is 5% by mass or more, the adhesive strength is increased, and when the content is 15% by mass or less, the viscosity is prevented from becoming too small.

<(A2) Methacryloyloxy group-containing compound>
In the resin paste composition of the present invention, (A2) a methacryloyloxy group-containing compound (hereinafter sometimes referred to as “component (A2)”) is an essential component. The resin paste composition not containing this (A2) methacryloyloxy group-containing compound has insufficient adhesion strength between the gold or silver surface and the silicon surface of the semiconductor element.

The (A2) methacryloyl group-containing compound used in the present invention is a component that can be said to be a matrix in which the filler (C) described later is dispersed, like the above-described (A1) acryloyl group-containing compound. A2) As the methacryloyl group-containing compound, a methacrylic acid ester compound can be used.
As (A2) methacryloyloxy group-containing compound used in the present invention, two methacryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms are contained in one molecule. If it has, there is no restriction in particular, for example, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1, Examples thereof include tricycloalkane group-containing dimethacrylate compounds such as 10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, cyclohexane dimethanol dimethacrylate, and tricyclodecane dimethanol dimethacrylate.

  5-15 mass% is preferable and, as for content of (A2) component in a resin paste composition, 6-12 mass% is especially preferable. When the content is 5% by mass or more, the adhesive strength is increased, and when the content is 15% by mass or less, the viscosity is prevented from becoming too small.

<(A1) component and (A2) component>
Thus, it is essential that the resin paste composition of the present invention contains both (A1) an acryloyloxy group-containing compound and (A2) a methacryloyloxy group-containing compound. The resin paste composition of the present invention has improved adhesive strength as compared with a resin paste composition containing only one of these two compounds due to the synergistic effect of these two compounds.
The content ratio of the component (A1) and the component (A2) is preferably (A1) component / (A2) component = 10/90 to 90/10, preferably 30/70 to mass ratio, from the viewpoint of further improving the adhesive strength. 70/30 is more preferable, and 40/60 to 60/40 is still more preferable.
<(A3) component>
It should be noted that the acryloyloxy group-containing compound and the methacryloyloxy group-containing compound other than the components (A1) and (A2) (hereinafter, other than the components (A1) and (A2) (to the extent that the effects of the present invention are not impaired) One or more of (meth) acryloyloxy group-containing compounds may be referred to as “component (A3)”.
<(A1) component, (A2) component and (A3) component>
The total amount of these (A1) component, (A2) component and (A3) component in the resin paste composition is preferably 10 to 35% by mass, more preferably 12 to 25% by mass. When the content is 10% by mass or more, the adhesive strength is increased, and when the content is 30% by mass or less, the viscosity is prevented from being excessively decreased.

<Flexible agent>
You may add a flexible agent to the resin paste composition of this invention as needed. By containing a flexible material, stress generated in the cured product of the resin paste composition due to thermal expansion or contraction of each member of the semiconductor device can be relaxed.
Although there is no restriction | limiting in particular in a flexible material, It is preferable to use liquid rubber or a thermoplastic resin.

(Liquid rubber)
Examples of the liquid rubber include liquid rubbers such as polybutadiene, epoxidized polybutadiene, maleated polybutadiene, acrylonitrile butadiene rubber, acrylonitrile butadiene rubber having a carboxy group, amino terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, and styrene butadiene rubber. Examples thereof include a resin having a polybutadiene skeleton.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resins such as polyvinyl acetate and polyalkyl acrylate, thermoplastic resins such as ε-caprolactone-modified polyester, phenoxy resin, and polyimide. Among these flexible materials, From the viewpoint of further reducing the elastic modulus of the cured product of the resin paste composition, epoxidized polybutadiene or acrylonitrile butadiene rubber having a carboxy group is preferable. The epoxidized polybutadiene can be easily obtained by epoxidizing a commercially available polybutadiene with a hydrogen peroxide solution and peracids. Examples of the epoxidized polybutadiene include B-1000, B-3000, G-1000, G-3000 (manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000, B-4000 ( (Nippon Oil Co., Ltd.), R-15HT, R-45HT, R-45M (Idemitsu Oil Co., Ltd.), Epolide PB-3600, Epolide PB-4700 (Made by Daicel Chemical Industries), etc. Is commercially available.

The oxirane oxygen concentration of the epoxidized polybutadiene is preferably 3% to 18%, and more preferably 5% to 15%.
In addition, from the viewpoint of further improving the die shear adhesive strength (strength necessary for pressing the needle from the side surface in the state where the semiconductor element is mounted on the support member and peeling the bonded semiconductor element), it has a carboxy group. Acrylonitrile butadiene rubber is more preferred. As the acrylonitrile butadiene rubber having a carboxy group, a compound represented by the general formula (I) is particularly preferable.

[In general formula (I), x and y each independently represents an integer of 1 or more. x / y is 95/5 to 50/50, and n is an integer of 5 to 50. ]
Examples of the butadiene-acrylonitrile copolymer having a carboxyl group represented by the general formula (I) include Hycar CTBN-2009 × 162, CTBN-1300 × 31, CTBN-1300 × 8, CTBN-1300 × 13, CTBN-1009SP-S and CTBNX-1300 × 9 (both manufactured by Ube Industries, Ltd.) are available as commercial products.
From the viewpoint of workability and adhesive strength, it is preferable to use epoxidized polybutadiene and acrylonitrile butadiene rubber having a carboxy group in combination.

(Number average molecular weight)
The liquid rubber preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is 500 or more, the flexibility effect is excellent, and when the number average molecular weight is 10,000 or less, the viscosity of the resin paste composition is small and the workability is excellent.
The thermoplastic resin preferably has a number average molecular weight of 10,000 to 300,000, more preferably 20,000 to 200,000. When the number average molecular weight is 10,000 or more, the flexibility effect is excellent, and when it is 300,000 or less, the viscosity of the resin paste composition does not increase and the workability is excellent.
The number average molecular weight is a value measured by a vapor pressure osmosis method or a value measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC).

(Content)
The content of the flexible agent in the resin paste composition is preferably 3 to 12% by mass, more preferably 4 to 10% by mass, and further preferably 5 to 8% by mass. When the blending amount is 3% by mass or more, the flexibility effect is improved, and when the blending amount is 12% by mass or less, it is prevented that the viscosity becomes too large and the workability of the resin paste composition is lowered.

<Other binder resin components>
The resin paste composition of the present invention may further contain an epoxy resin, a silicone resin, a urethane resin, an acrylic resin, etc. as other binder resin components.
However, from the viewpoint of suppressing an increase in the viscosity of the resin paste composition and reducing the volume resistivity, it is preferable that the aromatic epoxy resin is not substantially contained. Here, “substantially does not contain an aromatic epoxy resin” means that a small amount of aromatic epoxy resin may be present to such an extent that a rapid increase in volume resistivity is not observed.
Specifically, the content of the aromatic epoxy resin in the resin paste composition is preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. Moreover, it is especially preferable not to contain an aromatic epoxy resin.

<Amine compound>
The resin paste composition of the present invention may contain an amine compound. The amine compound is not particularly limited, but dicyandiamide, the following general formula (II)

(Wherein R ¹⁹ represents a divalent aromatic group such as an m-phenylene group or a p-phenylene group, or a linear or branched alkylene group having 2 to 12 carbon atoms), and a dibasic acid dihydrazide [ADH, PDH, SDH (all Nihon Finechem Co., Ltd., trade name)], microcapsule type curing agent composed of a reaction product of epoxy resin and amine compound [Novacure (Asahi Kasei Kogyo Co., Ltd., trade name)], etc. Imidazoles (Cureazole, 2P4MHZ, C17Z, 2PZ-OK, all of which are trade names manufactured by Shikoku Kasei Co., Ltd.) can also be used. Among them, dicyandiamide or imidazoles is preferable because the strength of the resin composition is improved, and dicyandiamide is particularly preferable.
These amine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the amine compound in the resin paste composition is preferably 0.05 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. When the content of the amine compound is 0.05% by mass or more, the curability is excellent, and when it is 1.5% by mass or less, the stability of the resin paste composition becomes good.

<(B) Polymerization initiator>
Since the resin paste composition of this invention contains the said (A1) component and (A2) component, it is necessary to contain the polymerization initiator (radical initiator) for radical polymerization of these components.
Although there is no restriction | limiting in particular as a radical initiator used for this invention, For example, a thermal-polymerization initiator and a photoinitiator are mentioned, These can also be used together.

Specific examples of the thermal polymerization initiator include azo radical initiators such as azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1,3, 3-tetramethylperoxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, di-t-butylperoxyiso Phthalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Examples include peroxides such as di (t-butylperoxy) hexyne and cumene hydroperoxide.
Specific examples of the photopolymerization initiator include acetophenones such as 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2,4- Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal, benzophenone, 4,4'-bis (diethylamino) benzophenone Benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.
The said polymerization initiator can be used individually or in combination of 2 or more types.

Among these polymerization initiators, a peroxide is preferable from the viewpoint of reducing voids called voids in the cured product of the resin paste composition, and from the viewpoint of curability and viscosity stability of the resin paste composition, The 10-hour half-life temperature of the peroxide is preferably 60 to 170 ° C, more preferably 65 to 120 ° C, and still more preferably 70 to 110 ° C.
Here, the half-life refers to the time required for the peroxide to decompose and the amount of active oxygen to be halved at a constant temperature. The 10-hour half-life temperature is a half-life of 10 hours. Indicates temperature.

The half-life can be measured, for example, as follows. First, using a solution that is relatively inert to radicals, such as benzene, a 0.1 mol / l concentration peroxide solution is prepared and sealed in a glass tube that has been purged with nitrogen. And it is immersed in the thermostat set to predetermined temperature, and is thermally decomposed. In general, the decomposition of peroxide can be treated approximately as a primary reaction, so the concentration x of the peroxide decomposed by the time after t, the decomposition rate constant k, the time t,
When the initial peroxide concentration is a, the following formula (i) is established.
dx / dt = k (ax) (i)
Then, when formula (i) is modified, formula (ii) is obtained.
ln a / (ax) = kt (ii)
Since the half-life is the time until the peroxide concentration is reduced to half of the initial value due to decomposition, the half-life is represented by t _1/2 and substituting a / 2 for x in the formula (ii), the formula (iii) )become.
kt _1/2 = ln2 (iii)
Therefore, the thermal decomposition is performed at a certain temperature, the decomposition rate constant k is obtained from the slope of the obtained straight line, and the half life (t _1/2 ) at that temperature can be obtained from the equation (iii).

  The content of the polymerization initiator in the resin paste composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and still more preferably 0.6 to 1% by mass. is there. When this content is 0.1% by mass or more, the curability is improved, and when it is 5% by mass or less, the volatile matter is reduced, and voids called voids are hardly generated in the cured product of the resin paste composition. Become.

<(C) Filler>
The resin paste composition of the present invention contains (C) a filler. By containing this (C) filler, the adhesive strength of the resin paste composition is improved.
There is no particular limitation on the filler (C), for example, gold, silver, copper, nickel, iron, aluminum, stainless steel, silicon oxide, boron nitride, aluminum oxide, aluminum borate, aluminum nitride, silicon nitride, silicon carbide. And the like. Among these, from the viewpoint of imparting electrical conductivity to the resin paste composition, metal powder such as gold, silver, copper, nickel, iron, aluminum, and stainless steel is preferable, and from the viewpoint of electrical conductivity and low cost. Silver powder and aluminum powder are preferable, and silver powder and aluminum powder are more preferably used in combination. In particular, by using these silver powder and aluminum powder in combination, it is possible to obtain a resin paste composition that is excellent in electrical conductivity, adhesion, and storage stability, and that is excellent in coating workability and mechanical properties.
Content of the (C) filler in a resin paste composition becomes like this. Preferably it is 60-85 mass%, More preferably, it is 65-80 mass%, More preferably, it is 70-80 mass%. Within the above range, the properties such as electrical conductivity and viscosity of the resin paste composition are more suitable as a die bonding material.

(Aluminum powder)
The average particle diameter of the aluminum powder is preferably 10 μm or less, more preferably 2 to 10 μm, still more preferably 2 to 9 μm, and particularly preferably 3 to 8 μm. When the average particle size of the aluminum powder is 10 μm or less, the paste uniformity and various physical properties are improved. When the average particle size of the aluminum powder is 2 μm or more, the dispersibility in the resin paste composition is excellent. In addition, the average particle diameter of aluminum powder is a cumulative mass 50% diameter (D ₅₀ ) measured by Microtrac X100 (laser diffraction diffraction method).
Further, the apparent density of the aluminum powder is preferably 0.40~1.20g / cm ^3, more preferably 0.55~0.95g / cm ^3. Within this range, the electrical conductivity, adhesion and storage stability are excellent, and the coating workability and mechanical properties are also excellent. The apparent specific gravity is a value measured according to JIS Z2504-2000.
Examples of the shape of the aluminum powder include particles, flakes, spheres, needles, irregular shapes, and the like, but particles are preferable.

(Silver powder)
The average particle diameter of silver powder, preferably 1 to 5 [mu] m, more preferably 2-4 [mu] m, the tap density of silver powder is preferably 3 to 6 g / cm ^3, more preferably a 4-5 g / cm ^3, silver powder The specific surface area is preferably 0.2 to ² m ² / g, more preferably 0.5 to 1 m ² / g. Within these ranges, the electrical conductivity, adhesion and storage stability are excellent, and the coating workability and mechanical properties are also excellent.
Here, the average particle diameter of the silver powder is the cumulative mass 50% diameter (D ₅₀ ) measured by Microtrack X100 (laser diffraction method). The tap density of silver powder is a value measured in accordance with JIS Z2512-2006. The specific surface area of the silver powder is a value measured according to the BET method (N ₂ gas) of JIS Z8830-2001.
Examples of the shape of the silver powder include granular shapes, flake shapes, spherical shapes, needle shapes, and irregular shapes, and flake shapes are preferable.

(Combination of aluminum powder and silver powder)
By using the aluminum powder and silver powder in combination, the cost is lower than when only silver powder is used, and it is more excellent in electrical conductivity, adhesiveness, and storage stability than when only aluminum powder is used, and A resin paste composition having excellent coating workability and mechanical properties can be obtained.
The mass ratio of the aluminum powder to be mixed to the silver powder (aluminum powder / silver powder) is preferably 2/8 to 8/2, more preferably 3/7 to 7/3, still more preferably 4/6 to 6 / 4. When the mass ratio of the aluminum powder to the silver powder is 8/2 or less, the resin paste composition has low resistance and high adhesive strength, and the viscosity is prevented from becoming too large, thereby improving workability. When it is 2/8 or more, the merit in cost becomes clearer.

<Coupling agent>
A coupling agent can be added to the resin paste composition of the present invention. There is no restriction | limiting in particular as a coupling agent, Various things, such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, a zircoaluminate coupling agent, are used.

  Specific examples of the coupling agent include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl-tris (2- Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N- Nylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) propyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropeno Xysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilyl isocyanate, dimethylsilyliso Silane coupling agents such as anate, phenylsilyl triisocyanate, tetraisocyanate silane, methylsilyl triisocyanate, vinylsilyl triisocyanate, ethoxysilane triisocyanate, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyro) Phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (Dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ) Ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumylphenyloxyacetate titanate, Titanate coupling agents such as diisostearoylethylene titanate, aluminum coupling agents such as acetoalkoxyaluminum diisopropionate, tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate , Zirconium acetylacetonate acetylacetone zirconium butyrate, There are zirconate-based coupling agents such as stearic acid zirconium butyrate.

  The content of the coupling agent in the resin paste composition is preferably 0.5 to 6% by mass, more preferably 1.0 to 5% by mass. When the content is 0.5% by mass or more, the effect of improving the adhesive strength is excellent, and when the content is 6% by mass or less, the volatile matter is reduced, and generation of voids in the cured product is suppressed.

<Other additive components>
The resin paste composition according to the present invention further includes a moisture absorbent such as calcium oxide and magnesium oxide, a fluorosurfactant, a nonionic surfactant, a wetting improver such as a higher fatty acid, silicone oil and the like as necessary. Diluents for adjusting the viscosity, such as an antifoaming agent and an ion trapping agent such as an inorganic ion exchanger, can be added as appropriate, alone or in combination of several kinds.

<Viscosity>
From the viewpoint of workability, the viscosity (25 ° C.) of the resin paste of the present invention is preferably 30 to 200 Pa · s, more preferably 40 to 150 Pa · s, and 40 to 80 Pa · s. Is particularly preferred. The viscosity is a value measured with a rotational viscometer in accordance with JIS Z8803-1991.

[Method for producing resin paste composition]
In order to produce the resin paste composition of the present invention, it is necessary together with the above (A1) acryloyloxy group-containing compound, (A2) methacryloyloxy group-containing compound, (B) a polymerization initiator, and (C) a filler. The above-mentioned various additives such as a flexible agent and a coupling agent used depending on the situation are put into a device that is appropriately combined with a dispersion / dissolution device such as a stirrer, hybrid mixer, planetary mixer, etc. Depending on the temperature, it may be heated, mixed, dissolved, pulverized and kneaded or dispersed to form a uniform paste.

[Semiconductor device]
The semiconductor device according to the present invention includes a support member, a semiconductor element (silicon chip) installed on the surface of the support member, and the support member and the semiconductor element interposed between the surface of the support member and the semiconductor element. It has the hardened | cured material of a resin paste composition, and the sealing material which seals a part of supporting member and a semiconductor element.
<Supporting member>
Examples of the support member include organic materials such as a lead frame such as a copper lead frame, a glass epoxy substrate (a substrate made of glass fiber reinforced epoxy resin), and a BT substrate (a BT resin-use substrate made of cyanate monomer and its oligomer and bismaleimide). A substrate is mentioned.
In the supporting member, the surface of the lead frame is preferably made of at least one of gold and silver. The gold on the surface of the lead frame is preferably one in which the surface of the support member body made of copper or the like is plated in three layers in the order of nickel / palladium / gold or two layers in the order of nickel / gold. A three-layer plating of / palladium / gold is more preferable. The silver on the surface of the lead frame is preferably silver-plated on the surface of the support member main body made of copper or the like, and more preferably silver-spot-plated. The resin paste composition of the present invention can be firmly bonded to the gold or silver surface.
<Encapsulant>
There is no restriction | limiting in particular in sealing material, For example, the molding (transfer molding) using sealing materials containing thermosetting resins, such as an epoxy resin, a silicone resin, a maleimide resin, an acrylic resin, potting, a premold, etc. are mentioned. .

[Method for Manufacturing Semiconductor Device]
There is no restriction | limiting in particular in the manufacturing method of the semiconductor manufacturing apparatus of this invention. For example, first, after applying the resin paste composition on the support member by the dispensing method, the semiconductor element is pressure-bonded, and then the resin paste composition is heated and cured using a heating device such as an oven or a heat block to obtain a cured product. . Next, after a wire bonding step according to a conventional method, a semiconductor device can be obtained by sealing the supporting member (except for the portion bonded to the substrate) and the semiconductor element by a conventional method with the above-described sealing material. .
The heat curing varies depending on the case of long-time curing at a low temperature or the case of rapid curing at a high temperature, but usually at a temperature of 150 to 220 ° C., preferably 180 to 200 ° C., preferably 30 seconds to 2 hours, preferably It is preferable to carry out for 1 hour to 1 hour 30 minutes.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited by this.

[Various compounds to be contained in the resin paste composition]
Various compounds used in Examples and Comparative Examples are as follows.
<(A1) component>
A-DCP (Tridecane dimethanol diacrylate, manufactured by Shin Nakamura Kogyo Co., Ltd., a compound represented by the following structure)

<(A2) component>
(1) DCP (tridecane dimethanol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by the following structure)

(2) FA-124M (1,4-butanediol dimethacrylate, manufactured by Hitachi Chemical Co., Ltd., a compound represented by the following structure)

(3) FA-125M (Neopentyl glycol dimethacrylate, manufactured by Hitachi Chemical Co., Ltd., a compound represented by the following structure)

<(A3) component>
SR-349 (EO-modified bisphenol A diacrylate, manufactured by Sartomer, a compound represented by the following structure)

<(B) Polymerization initiator>
Trigonox 22-70E (manufactured by Kayaku Akzo Corporation, 1,1-bis (tert-butylperoxy) cyclohexane, 10 hour half-life temperature; 91 ° C.)
<(C) Filler>
(1) Aluminum powder VA-2000 (manufactured by Yamaishi Metal Co., Ltd., shape: granular, average particle size = 6.7 μm)
(2) Silver powder AgC-212DH (Fukuda Metal Foil Powder Co., Ltd., shape: flake, average particle size: 2.9 μm)

<Flexible material>
(1) CTBN-1009SP-S (Ube Industries, Ltd., acrylonitrile polybutadiene copolymer having a carboxy group)
(2) Epolide PB-4700 (manufactured by Daicel Chemical Industries, Ltd., trade name of epoxidized polybutadiene, epoxy equivalent: 152.4 to 177.8, number average molecular weight = 3500)
<Amine compound>
Dicy (Dicyandiamide, manufactured by Japan Epoxy Resin Co., Ltd.)
<Coupling agent>
(1) KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane)
(2) SZ-6030 (Toray Dow Corning, 3-methacryloxypropyltrimethoxysilane)

[Examples 1 to 3 Comparative Examples 1 to 5]
Each material was mixed at the blending ratio shown in Table 1 and kneaded using a planetary mixer, and then defoamed at 666.61 Pa (5 Torr) or less for 10 minutes to obtain a resin paste composition. . The characteristics (die shear adhesive strength, volume resistivity) of this resin paste composition were examined by the following methods. The results are shown in Table 1.

(1) Die shear bonding strength Resin paste composition is nickel / palladium / gold plated copper substrate (adhered to silicon chip: gold), silver spot plated copper substrate (adhered to silicon chip: silver), and silver ring plating About 0.5 mg is applied to the surface of a copper substrate (adhered to a silicon chip: copper), a 3 mm × 3 mm silicon chip (thickness: about 0.4 mm) is pressure-bonded thereon, and further up to 180 ° C. in an oven. The temperature was raised in 30 minutes and cured at 180 ° C. for 1 hour. This was measured for shear adhesive strength (MPa) when held at 260 ° C. for 20 seconds using an automatic adhesive strength tester (BT4000, manufactured by Dage). The die shear adhesive strength was measured for 10 test pieces, and the average value was defined as the die shear adhesive strength.

(2) Volume resistivity The volume resistivity of the cured product of the resin paste composition was measured by the procedure shown in FIG. FIG. 1 is a plan view illustrating a method for measuring volume resistivity.
Three paper tapes 2 (manufactured by Nitto Denko CS System) on the surface of slide glass 1 (manufactured by Tokyo Glass Equipment Co., Ltd., dimensions = 76 × 26 mm, thickness = 0.9 to 1.2 mm) (FIG. 1A) , No. 7210F, Dimension width = 18 mm, Thickness = 0.10 mm) are attached in parallel to each other at an interval so that the exposed portion 3 (width) on the surface of the slide glass 1 is placed between these three paper tapes 2. 2 mm) was formed (FIG. 1B). The resin paste composition 4a was placed on these exposed portions 3 (FIG. 1 (c)) and stretched flat with another slide glass or the like (FIG. 1 (d)). Next, the paper tape 2 was peeled off and cured in an oven at 180 ° C. for 1 hour to obtain two linear cured products 4 parallel to each other on the surface of the slide glass 1 (FIG. 1 (e)). The volume resistivity (Ω · cm) of these cured products 4 was measured at a temperature of 23 ° C. using a digital multimeter (TR6846, manufactured by ADVANTEST).

(3) Viscosity stability The viscosity (Pa · s) at 25 ° C. was measured at 0.5 rpm using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) and a 3 ° cone rotor. This measurement was performed immediately after the production of the resin paste composition (initial stage), 1 day after production (1st day), 3 days later (3rd day), and 7 days later (7th day).

From the results of Table 1, the resin paste composition containing the conductive filler of the present invention is for any of nickel / palladium / gold plated substrate (adhered body: gold) and silver spot plated substrate (adhered body: silver). It was also confirmed that it has high adhesive strength. Moreover, it has confirmed that the resin paste composition containing the electroconductive filler of this invention had the adhesive strength equivalent to a comparative example also with respect to a silver ring plating board | substrate (adhered body: copper).
The resin paste compositions (Examples 1 to 3) containing the conductive filler of the present invention have a volume resistivity comparable to that of Comparative Examples 1 to 5, and viscosity stability to Comparative Examples 1 to 2, 4 to 5 It was confirmed that the volume resistivity and viscosity stability were excellent.

DESCRIPTION OF SYMBOLS 1 Slide glass 2 Paper tape 3 Exposed part 4 Hardened | cured material 4a Resin paste composition

Claims (10)

(A1) In one molecule, an acryloyloxy group-containing compound having two acryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms,
(A2) In one molecule, a methacryloyloxy group-containing compound having two methacryloyloxy groups and an alicyclic structure having 5 to 20 carbon atoms or an aliphatic structure having 4 to 20 carbon atoms,
A resin paste composition containing (B) a polymerization initiator, and (C) a filler.   The resin paste composition according to claim 1, further comprising a flexible agent.   Furthermore, the resin paste composition of Claim 1 or 2 containing an amine compound.   The resin paste composition according to any one of claims 1 to 3, wherein the filler contains silver powder and aluminum powder.   The resin paste composition according to claim 4, wherein the average particle diameter of the aluminum powder is 2 to 10 μm.   The resin paste composition according to claim 4 or 5, wherein the silver powder has an average particle diameter of 1 to 5 µm.   The resin paste composition according to any one of claims 4 to 6, wherein a mass ratio of the aluminum powder to the silver powder (aluminum powder / silver powder) is 2/8 to 8/2.   The resin paste composition according to any one of claims 1 to 7, which does not substantially contain an aromatic epoxy resin. Support member,
A semiconductor element installed on the surface of the support member;
The cured product of the resin paste composition according to any one of claims 1 to 8, wherein the support member and the semiconductor element are fixed between the surface of the support member and the semiconductor element, and A sealing material for sealing a part of the support member and the semiconductor element;
A semiconductor device.   The semiconductor device according to claim 9, wherein an installation surface of the support member with the cured product is a surface made of at least one of gold and silver.

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