TW201543584A - Die-attach paste for semiconductors and semiconductor package - Google Patents

Abstract

Provided are a die-attach paste for semiconductors and a semiconductor package, whereby a semiconductor package can be produced that maintains coating properties, is capable of suppressing bleeding after coating by B-staging, is capable of obtaining sufficient adhesiveness even without heating during die-bonding, and has high reliability. The die-attach paste for semiconductors includes: a (meth) acryloyl group-containing compound (1); a ring structure-containing compound (2) containing an oxirane ring structure or an oxetane ring structure; a maleic anhydride-modified polyolefin (3); and a photopolymerizable initiator (4). Furthermore, a highly reliable, highly integrated semiconductor package can be produced by coating this semiconductor die-attach paste on to a support member or a die, then B-staging by ultraviolet irradiation, then die-bonding.

Description

Die attach paste for semiconductors and semiconductor packages

The present invention relates to a die attach paste for a semiconductor and a semiconductor package manufactured using the die attach paste for a semiconductor.

As a semiconductor wafer (hereinafter referred to as "die") such as a bonding IC or an LSI, and a supporting member such as a lead frame or an insulating supporting substrate, a bonding material for manufacturing a semiconductor package is sealed, except for an Au-Si eutectic alloy. In addition to soldering, pastes, films, and the like which use a resin as a main raw material have been known.

Although the Au-Si eutectic alloy has high heat resistance and moisture resistance, the elastic modulus is large, and the stress of expansion and contraction of other members due to the heat history is easily broken and expensive. Although the welding is inexpensive, the heat resistance is insufficient, the modulus of elasticity is high, and it is also easily broken.

A paste containing a resin as a main raw material (hereinafter referred to as "grain adhesion paste") and a film (hereinafter referred to as "die adhesion film") have sufficient heat resistance, moisture resistance, and elastic modulus, and can alleviate heat The stress caused by the expansion and contraction caused by the resume is widely used. However, when the grain adhesion paste becomes a viscosity considering coating properties, it is easy to wet and spread, and the same package is mounted in plural. In the case of a package of a crystal grain (hereinafter referred to as a "multi-die package"), since it is necessary to obtain the distance between the crystal grains, it is difficult to cope with the high integration of the multi-die package.

Further, the die-adhesive film must also be used in a method of cutting out the size corresponding to the grain size or a method of attaching without a bubble. In addition, the cost is also unfavorable because the allowance generated when cutting out is discarded. Further, in the step of bonding the crystal grains and the supporting member (hereinafter referred to as "grain bonding"), it is necessary to apply heat to the crystal grains, and there is a disadvantage that the reliability of the semiconductor package is lowered by giving a heat history to the crystal grains.

As a method for solving the disadvantages of such a die-adhesive or die-adhesive film, the proposal has a B-stage. The term "B-staged" refers to a method in which only one of the hardening components is partially cured by volatilization of the solvent contained in the die-adhesive paste, and the adhesion of the die-adhesive paste is applied or thixotropy by the coating. Or a process that maintains the hardness of the shape and prevents the wet spread of the die adhesion paste.

As a B-stage of the die attach paste, a method of applying a grain thickness to a certain thickness and then semi-curing by irradiation with ultraviolet rays has been proposed in Patent Documents 1 and 2. The techniques proposed in Patent Documents 1 and 2 correspond to the operation of adhering the die adhesion paste to a solid which can maintain the hardness of the shape, that is, the B-stage of the applied die attach paste is formed into a die attach film. Technology. According to such techniques, although it is possible to eliminate the incorporation of air bubbles when the die attach film is attached, or to discard the margin when cutting out, there is a heat history of the die by heat pressing, thereby making the semiconductor package. The problem of reduced reliability can not be solved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-258425

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-270130

The present invention has been made in view of the problems of the prior art described above, and provides a method of maintaining the coating property and suppressing the spread of moisture after coating by the B-stage, and even if the crystal grains are not heated, In order to obtain sufficient adhesion, it is possible to manufacture a semiconductor die bond paste and a semiconductor package for a highly reliable semiconductor package.

As a result of repeated studies to solve the above problems, the present inventors have found a ring-containing structure including a (meth)acryl fluorenyl group-containing compound and an ethylene oxide (Oxirane) ring structure or an oxypropylene (Oxetane) ring structure. The compound, the maleic anhydride-modified polyolefin, and the photopolymerization initiator are used for the semiconductor die adhesion paste, and the coating property can be maintained, and the B-stage can suppress the wet diffusion after the coating, and when the crystal grains are formed, Even if it is not heated, sufficient adhesion can be obtained, and the present invention is completed.

That is, the aspect of the present invention is as described in [1] to [15] below.

[1] A die attach paste for a semiconductor characterized by containing Compound (1), a fluorenyl group-containing compound (1), a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure (2), a maleic anhydride-modified polyolefin (3), and a photopolymerization initiation Agent (4).

[2] The die attach paste for a semiconductor according to [1], wherein the blending amount of the (meth)acrylonitrile group-containing compound (1) is 5% by mass or more and 80% by mass based on the total hardening component. Hereinafter, the blending amount of the compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure is the total number of oxirane ring structures or propylene oxide ring structures relative to those derived from the aforementioned horses. The ratio of the total number of the carboxylic anhydride structures of the maleic anhydride of the anhydride-modified polyolefin (3) is 2.8 to 0.4; the blending amount of the maleic anhydride-modified polyolefin (3) is 20% by mass or more and 80% by mass or less; the blending amount of the photopolymerization initiator (4) is 0.01 parts by mass or more and 5 parts by mass based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group. Below the mass.

[3] The die attach paste for a semiconductor according to [1] or [2], which further comprises a thermal radical generating agent (5).

[4] The die attach paste for a semiconductor according to [3], wherein the amount of the thermal radical generating agent (5) is blended with respect to 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group. It is 0.1 part by mass or more and 10 parts by mass or less.

[5] The die attach paste for a semiconductor according to [3] or [4] wherein the thermal radical generating agent (5) is an organic peroxide.

[6] The die attach paste for a semiconductor according to [5], wherein the thermal radical generating agent (5) is a dialkyl peroxide or a peroxyester.

[7] The die attach paste for a semiconductor according to any one of [3] to [6] wherein the thermal radical generating agent (5) has a one-minute half-life temperature of 120 ° C or more and 200 ° C or less.

[8] The die attach paste for a semiconductor according to any one of [1] to [7] further comprising a thermosetting accelerator (6).

[9] The die attach paste for a semiconductor according to any one of [1] to [8] further comprising a filler (7).

[10] The die attach paste for a semiconductor according to any one of [1] to [9] wherein at least a part of the (meth)acrylonitrile group-containing compound (1) contains a plurality of (meth) propylene A thiol-containing compound having a polyfunctional (meth) acrylonitrile group.

[11] The die attach paste for a semiconductor according to any one of [1] to [10] wherein at least a part of the (meth)acryl fluorenyl group-containing compound (1) is (meth) propylene hydride. The (meth)acrylonitrile-containing compound (8) containing the same in the same molecule as the oxirane ring structure or the propylene oxide ring structure.

[12] The die attach paste for a semiconductor according to any one of [1] to [11] wherein the maleic anhydride-modified polyolefin (3) is a copolymerized prepolymerized diene, and a maleic anhydride .

[13] The die attach paste for a semiconductor according to any one of [1] to [12] wherein the maleic anhydride-modified polyolefin (3) has a number average molecular weight of more than 5,000.

[14] The die attach paste for a semiconductor according to any one of [1] to [13] wherein the photopolymerization initiator (4) is an alkylphenone photopolymerization initiator and a mercaptophosphine oxidation At least one of the photopolymerization initiators.

[15] A semiconductor package produced by using the die attach paste for a semiconductor according to any one of [1] to [14].

The die attach paste for a semiconductor of the present invention can maintain the coating property while suppressing the wet spread after coating by the B-stage, and has a high integration of the multi-die package, and the crystal grains are bonded. Even if it is not heated, a sufficient adhesive effect can be obtained.

Moreover, by using the die attach paste for a semiconductor of the present invention, it is possible to manufacture a semiconductor package having high reliability and high integration, and the semiconductor package of the present invention has high reliability and high integration.

Hereinafter, embodiments of the present invention will be described in detail. In the present invention, the term "(meth)acryl fluorenyl" means propylene fluorenyl group and/or methacryl fluorenyl group.

<Semiconductor die attach paste>

The die attach paste for a semiconductor of the present invention comprises a compound (1) containing a (meth)acryl fluorenyl group, a compound having a ring structure containing an oxirane ring structure or a propylene oxide ring structure, and a Malay An acid anhydride modified polyolefin (3), and a photopolymerization initiator (4).

First, the compound (1) containing a (meth) acrylonitrile group will be described.

The component is a hardening component which is radically polymerized and hardened, and is not particularly limited as long as it is a compound containing a (meth)acryl fluorenyl group. However, the compound (1) containing a (meth) acrylonitrile group excludes a (meth) acrylonitrile group among the decane coupling agents (9) described later. That is, in the case where the ruthenium coupling agent (9) is contained in the die attach paste for a semiconductor of the present invention, when the decane coupling agent (9) contains a (meth) acrylonitrile group, it has a (meth) propylene group. The decyl cyclane coupling agent is included in the decane coupling agent (9) and is not included in the (meth) acrylonitrile-containing compound (1).

Examples of the (meth)acrylonitrile group-containing compound (1) include polyol poly(meth)acrylate, epoxy (meth)acrylate, and ethyl urethane (meth)acrylate. , (meth) acrylate monomer, and the like.

The polyhydric alcohol (meth) acrylate refers to a polyhydric alcohol, an ester compound with acrylic acid or methacrylic acid. The polyol selected herein is not particularly limited, and examples thereof include a chain-like hydrogenated dimer diol, 1,3-propane diol, 1,4-butanediol, and 1,3-butylene glycol. 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9 -decanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 1, A chain aliphatic polyol such as 12-dodecanediol, a polyolefin polyol, or a hydrogenated polyolefin polyol.

Further, examples of the polyhydric alcohol include a hydrogenated dimer diol having an alicyclic structure, a hydrogenated bisphenol A olefin oxide adduct, a hydrogenated bisphenol F olefin oxide adduct, and a hydrogenated bisphenol olefin oxide adduct. 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclo[5.2.1.02,6]decane dimethanol, 2-methylcyclohexane-1,1-dimethanol, etc. Diversified with alicyclic structure alcohol.

Further, examples of the polyhydric alcohol include a trimer triol, p-benzenedimethanol, a bisphenol A olefin oxide adduct, a bisphenol F olefin oxide adduct, and a bisphenol olefin oxide adduct. Aromatic ring polyol. Further, examples thereof include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and examples thereof include polyhexamethylene adipate, polyhexamethylene succinate, and polyhexene. A polyester polyol such as an ester.

Further, examples of the polyhydric alcohol include α,ω-poly(1,6-exexhexyl carbonate) glycol, α,ω-poly(3-methyl-1,5-exopentyl carbonate) glycol, and α. , ω-poly[(1,6-extensionyl:3-methyl-pentamethylene)carbonate]diol, α,ω-poly[(1,9-extension: 2-methyl-1) (poly)carbonate diol such as 8-(octyl)carbonate]diol, and further, a polycondensation of a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol Ester polyol. These polyols may be used singly or in combination of two or more kinds as appropriate.

Moreover, from the viewpoint of ensuring the elastic modulus after hardening, a polyol having an alicyclic structure, a polyhydric alcohol having an aromatic ring, a (poly)carbonate diol, and a polyester polyol are preferable. More preferably, it is a polyol having an aromatic ring. For example, M-208 (manufactured by Toagosei Co., Ltd.) and M-211B (manufactured by Toagosei Co., Ltd.), which is a commercial product of a poly(poly)poly(meth)acrylate derived from a polyhydric alcohol having an aromatic ring, may be mentioned. ), FA-321A (made by Hitachi Chemical Co., Ltd.), FA-324A (made by Hitachi Chemical Co., Ltd.), Light Acrylate BP-4EAL (made by Kyoeisha Chemical Co., Ltd.), Light Acrylate BP-4PA (Kyoeisha Chemical Co., Ltd.) Limited company System) and so on.

Further, the epoxy group (meth) acrylate refers to a compound obtained by adding acrylic acid or methacrylic acid by an epoxy group terminal epoxy group. The epoxy resin selected at this time is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolak type epoxy resin, and hydrogenated phenol no. A varnish type epoxy resin, a glycidyl ester type epoxy resin, a biphenyl type epoxy resin, a hydrogenated biphenyl type epoxy resin, or the like. These may be used singly or in combination of two or more kinds as appropriate.

Examples of the commercially available epoxy group (meth) acrylate include epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL 600 (manufactured by Daicel-Cytec Co., Ltd.), and EBECRYL 6040 (Daicel-Cytec). Co., Ltd.) and so on.

The term "ethyl methacrylate (meth) acrylate" refers to a reaction between a polyol and a polyisocyanate and a hydroxyl group-containing (meth) acrylate, or a polyol and an isocyanate group-containing (meth) acrylate. The compound obtained by carrying out the reaction of the ester. The polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, and isocyanate group-containing (meth) acrylate selected at this time are not particularly limited.

The polyol is the same as the polyol used in the polyol poly(meth)acrylate. Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanatemethyl)cyclohexane. 1,4-bis(isocyanatemethyl)cyclohexane, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, diphenylmethane-4,4 ' diisocyanate, 1 , 3-phenyldimethyl diisocyanate, 1,4- phenyldimethyl diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethyl six Methylene diisocyanate, 2,2,4-trimethylhexane methylene diisocyanate, norbornane diisocyanate, and the like. These may be used singly or in combination of two or more kinds as appropriate.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl. Acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyl Ethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-benzene Oxypropyl methacrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl methacrylate, and the like. These may be used singly or in combination of two or more kinds as appropriate.

Examples of the (meth) acrylate containing an isocyanate group include 2-isocyanate ethyl acrylate and 2-isocyanate ethyl methacrylate. These may be used singly or in combination of two or more kinds as appropriate.

Ethyl urethane (meth) acrylate in the presence or absence of a known urethane catalyzed catalyst such as dibutyltin dilaurate or dioctyltin dilaurate Synthesizing a polyol with a polyisocyanate and a hydroxyl group-containing (meth) acrylate, or reacting a polyol with an isocyanate group-containing (meth) acrylate, but storing it in a catalyst It is preferred in the sense that the reaction is shortened in the reaction. However, when the die attach paste for semiconductors is actually used as a cured film, when a catalyst is used excessively, the amount of the catalyst is adversely affected by the physical properties of the cured film. The total amount of the polyol and the polyisocyanate and the hydroxyl group-containing (meth) acrylate or the polyol and the isocyanate group-containing (meth) acrylate is preferably 0.001 to 1 part by mass.

Further, in the case where the die attach paste for a semiconductor of the present invention contains an alkoxyalkylene group, the hydrolysis reaction of the urethane-based catalyzed catalyst is a catalytic alkoxyalkyl group. In such a case, it is necessary to consider the balance between the time stability of the die attach paste for a semiconductor of the present invention and the adhesion to a supporting member (for example, a lead frame or a substrate), and the amount of use at this time is relative to the polyol and The total amount of the polyisocyanate and the hydroxyl group-containing (meth) acrylate, or the polyol and the isocyanate group-containing (meth) acrylate is preferably 0.003 to 0.2 parts by mass, more preferably 0.005 to 0.15 by mass. Share. When the amount of the catalyst is 0.001 parts by mass or more, the effect of the addition of the catalyst is appropriately exhibited, and if it is 1 part by mass or less, as described above, the physical property value actually used as the cured film becomes good.

In the (meth) acrylate monomer of the present specification, the poly(poly)poly(meth)acrylate and the epoxy group (methyl group) are removed from the above-mentioned (meth) fluorenyl group-containing compound (1). a compound of an acrylate and the aforementioned ethyl methacrylate (meth) acrylate.

Examples of the (meth) acrylate monomer include glycidyl acrylate, tetrahydrofurfuryl acrylate, and glycidyl methacrylate. (Meth)propenyl group-containing compound having a cyclic ether group such as tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, isodecyl acrylate, dicyclopentenyl acrylate, dicyclopentene Base oxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, isodecyl methacrylate Ester, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentylethyl methacrylate, 4- Monofunctional (meth) acrylonitrile-containing compound having a cyclic aliphatic group such as tert-butylcyclohexyl methacrylate, lauryl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate , isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, isoamyl acrylate, lauryl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate , isobutyl methacrylate, tert-butyl methacrylate, isooctyl Monofunctional (meth) acrylonitrile-containing compound having a chain aliphatic group such as methacrylate or isoamyl methacrylate, benzyl acrylate, phenoxyethyl acrylate, benzyl group Monofunctional (meth) acrylonitrile-containing compound having an aromatic ring, such as acrylate, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, etc. Diol diacrylate, decanediol diacrylate, decanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate A polyfunctional (meth) acrylonitrile-containing compound such as an ester, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate. Still, the above-mentioned monofunctional (meth) propylene sulfhydryl group The compound refers to a compound containing a (meth) acryl fluorenyl group containing a (meth) acryl fluorenyl group, and the above-mentioned compound containing a polyfunctional (meth) acryl fluorenyl group means a complex (methyl group). a compound containing a (meth)acrylonitrile group of an acrylonitrile group.

The amount of the (meth)acryl fluorenyl group-containing compound (1) used in the die attach paste for a semiconductor of the present invention is preferably from 5 to 80% by mass, more preferably from 10 to 60% by mass based on the total hardening component. %, more preferably 15 to 50% by mass. When the amount of the compound (1) containing the (meth) acrylonitrile group is 80% by mass or less based on the total hardening component, the adhesion of the cured product of the semiconductor die bond paste to the support member is good. . In addition, when the amount of the (meth) fluorenyl group-containing compound (1) is 5% by mass or more based on the total hardening component, the viscosity of the semiconductor die-bonding paste is improved, and the handling becomes easy. .

In addition, the term "hardening component" as used in the present specification means a compound polymerizable by radical polymerization and/or a compound having a ring structure having an oxirane ring structure or a propylene oxide ring structure (2) And/or a compound which can react with an oxirane ring structure or a propylene oxide ring structure, and the term "all-hardening component" means the total amount of the hardening component. Compound (1) containing (meth) acrylonitrile group, compound (2) containing ring structure having oxirane ring structure or propylene oxide ring structure, and maleic anhydride modified polyolefin (3) described later Contained in hardening ingredients.

P-styryltrimethoxydecane, p-styryltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropene oxime in the decane coupling agent (9) described later Oxypropyl trimethoxy decane, 3-propane Isomethoxypropyltriethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropylmethyldimethoxydecane, 3-methylpropene oxime Free radical polymerization of oxypropylmethyldimethoxydecane, 3-propenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane The unsaturated alkyl decane coupling agent is also included in the hardening component.

The (meth)acrylonitrile group-containing compound (1) used in the present invention preferably contains the (meth)acrylonyl group and the oxirane ring structure or the propylene oxide ring structure in the same molecule. A (meth)acryloyl group-containing compound (8). a (meth)acrylonitrile group-containing compound (8) containing both a (meth) acrylonitrile group and an oxirane ring structure or a propylene oxide ring structure in the same molecule, if The compound in which the acrylonitrile group and the oxirane ring structure or the propylene oxide ring structure are contained in the same molecule is not particularly limited.

However, the (meth) acrylonitrile-containing compound (8) containing the (meth) acrylonitrile group and the oxirane ring structure or the propylene oxide ring structure in the same molecule is not included in the following description. A compound (2) having a ring-containing structure of an oxirane ring structure or a propylene oxide ring structure. In other words, the die attach paste for a semiconductor of the present invention contains (meth) propylene containing (meth) propylene fluorenyl group, an oxirane ring structure or a propylene oxide ring structure contained in the same molecule. In the case of the fluorenyl compound (8), the (meth) acrylonitrile-containing compound (8) containing the (meth) acrylonitrile group and the oxirane ring structure or the propylene oxide ring structure in the same molecule ), which is included in the compound (1) containing a (meth) acrylonitrile group, and is not included in the oxirane ring. A compound (2) having a ring structure constructed of a propylene oxide ring structure.

The (meth)acryl fluorenyl group-containing compound (8) in which the (meth) acrylonitrile group and the oxirane ring structure or the propylene oxide ring structure are contained in the same molecule may be exemplified by the above-mentioned polyol. Poly(meth)acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or (meth) acrylate monomer containing an oxirane ring structure or ring An oxypropane ring structure or the like.

For example, a polyhydric alcohol (meth) acrylate or a urethane (meth) acrylate derived from a polyol containing an oxirane ring structure or a propylene oxide ring structure, or an epoxy group may be cited. Epoxy (meth) acrylate derived from an epoxy resin of an ethane ring structure or a propylene oxide ring structure. These can be obtained, for example, by setting the total number of oxirane ring structures or propylene oxide ring structures contained therein to the ratio of the total number of acrylic acid or methacrylic acid to be reacted to be greater than 1. Further, for example, examples of the (meth) acrylate monomer having an oxirane ring structure or a propylene oxide ring structure include glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate. Glycidyl ether and the like.

In the die attach paste for a semiconductor of the present invention, a (meth)acryl fluorenyl group-containing compound containing the (meth)acryl fluorenyl group, the oxirane ring structure or the propylene oxide ring structure in the same molecule The amount of use of the (8) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30% by mass based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group. More than one. a (meth)acryl oxime containing the (meth) acrylonitrile group and the oxirane ring structure or the propylene oxide ring structure contained in the same molecule When the amount of the compound (8) to be used is 100 parts by mass or more based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group, the semiconductor die paste can be hardened. The elastic modulus of the object becomes good.

Next, the compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure will be described. The compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure is not particularly limited as long as it is a compound having an oxirane ring structure or a propylene oxide ring structure.

Examples of the compound containing an oxirane ring structure or a propylene oxide ring structure include epichlorohydrin adducts such as alcohols, amines, and carboxylic acids, olefin oxides, cyclic adducts of ketones and olefins, and epoxy resins. Specific examples of the propanol derivative and the like include an epoxy resin used in the above epoxy (meth) acrylate, or 2-ethylhexyl propylene oxide, benzodimethyl propylene oxide, and a ring. Oxypropane resin. The compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure is preferably a bifunctional or higher, from the viewpoint of the crosslinking density of the die-bonded paste hardened material for a semiconductor of the present invention. Among them, an epoxy resin is preferred.

The compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure in the die attach paste for a semiconductor of the present invention is preferably an oxirane ring structure or propylene oxide. The ratio of the total number of ring structures to the total number of carboxylic anhydride structures derived from maleic anhydride of the maleic anhydride-modified polyolefin (3) described later is 2.8 to 0.4, more preferably 2.0 to 1.2. The ratio of the total number of oxirane ring structures or propylene oxide ring structures to the total number of carboxylic anhydride structures derived from maleic anhydride is 2.8 to 0.4, The modulus of elasticity of the cured product of the die adhesion paste for a semiconductor of the present invention can be improved.

Next, the maleic anhydride-modified polyolefin (3) will be described.

The maleic anhydride-modified polyolefin (3) can be obtained, for example, by copolymerization of maleic anhydride with an unsaturated hydrocarbon. Examples of the unsaturated hydrocarbon include an olefin such as an α-olefin or a diene. Examples of the α-olefin include ethylene, propylene, and 1-butene. Examples of the diene include butadiene and isoprene. Further, the maleic anhydride-modified polyolefin (3) may be produced by copolymerizing at least one of the above-mentioned unsaturated hydrocarbons by copolymerization or copolymerization with maleic anhydride.

The unsaturated hydrocarbon copolymerized with maleic anhydride is preferably a compound having a conjugated double bond, more preferably a prepolymerized butadiene or from the viewpoint of stress relaxation of a cured product of a die bond for a semiconductor. Isoprene, or pre-polymerized butadiene and isoprene. Further, the maleic anhydride-modified polyolefin (3) is preferably one having an unsaturated divalent hydrocarbon group. Further, the maleic anhydride-modified polyolefin (3) is contained in a compound obtained by prepolymerizing butadiene or isoprene or prepolymerizing butadiene with isoprene to graft maleic anhydride. .

As a commercial item of the maleic anhydride-modified polyolefin, DIACARNA (made by Mitsubishi Chemical Corporation), M-1000-80 (made by Nippon Petrochemical Co., Ltd.), Ricon MA (made by CRAYVALLEY Co., Ltd.), etc. are mentioned.

The number average molecular weight of the maleic anhydride-modified polyolefin (3) is preferably more than 2,000 and less than 20,000, more preferably more than 5,000 and less than 10,000. When the number average molecular weight of the maleic anhydride-modified polyolefin (3) is more than 2,000, the elastic modulus and stress relaxation property of the cured product of the die-adhesive paste for semiconductor of the present invention can be improved. Further, when the number average molecular weight of the maleic anhydride-modified polyolefin is 20,000 or less, the viscosity of the die adhesion paste for a semiconductor can be improved, and the handling can be facilitated.

Further, the number average molecular weight can be measured by a polystyrene conversion algorithm or the like by gel permeation chromatography (GPC).

The anhydride equivalent of the maleic anhydride-modified polyolefin (3) is preferably 300 or more and 1200 or less. When the anhydride equivalent of the maleic anhydride-modified polyolefin (3) is 300 or more, the viscosity of the die attach paste for a semiconductor of the present invention can be improved, and the handling can be facilitated. In addition, when the anhydride equivalent of the maleic anhydride-modified polyolefin (3) is 1200 or less, the modulus of elasticity of the cured product of the die bond for semiconductor can be improved.

The amount of the maleic anhydride-modified polyolefin (3) used in the die attach paste for a semiconductor of the present invention is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass based on the total hardening component. When the amount of the maleic anhydride-modified polyolefin (3) is 20% by mass or more based on the total hardening component, the elastic modulus and stress relaxation property of the cured product of the die bond for a semiconductor can be improved. In addition, when the amount of the maleic anhydride-modified polyolefin (3) is 80% by mass or less based on the total hardening component, the viscosity of the semiconductor die bond paste can be improved, and the handling can be facilitated.

Next, the photopolymerization initiator (4) will be described.

If the photopolymerization initiator is by near infrared rays, visible light, or ultraviolet rays Irradiation of light, which produces free radicals that contribute to the initiation of free radical polymerization. The compound is not particularly limited.

Further, as the photopolymerization initiator, a metallocene compound can also be used. As the metallocene compound, a transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, or the like can be used, for example, Bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(pyrrol-1-yl)phenyl]titanium is exemplified.

More preferably, the photopolymerization initiator used in the present invention is an alkylphenone photopolymerization initiator, a mercaptophosphine oxide photopolymerization initiator, and the photopolymerization initiators can be used alone. Alternatively, two or more types may be used in combination.

Examples of the alkylphenone-based photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and 1-hydroxycyclohexylphenyl. Ketone, 1,2-hydroxy-2-methyl-1-phenylpropan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, 2-hydroxyl -2-methyl-1-(4-isopropylphenyl)acetone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)acetone, 2-hydroxy-2-methyl 1-[(2-hydroxyethoxy)phenyl]acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-( Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)-1-butanone, 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholinyl-1-propanone, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl) Ether, benzoin isobutyl ether, benzoin phenyl ether, benzyl dimethyl ketal, and the like.

Among the alkylphenone-based photopolymerization initiators, α-amines are more preferred. Alkyl benzophenone photopolymerization initiator. Examples of the α-aminoalkylphenone photopolymerization initiator include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2- (Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinyl-1-propanone and the like. These may be used singly or in combination of two or more kinds as appropriate.

Further, examples of the mercaptophosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and 2,6-dimethoxybenzamide. Phenylphosphine oxide, 2,6-dichlorobenzhydryldiphenylphosphine oxide, 2,4,6-trimethylbenzimidylmethoxyphenylphosphine oxide, 2,4,6 -trimethylbenzimidylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzhydryldiphenylphosphine oxide, bis-(2,6-dichlorobenzene Thiolyl)phenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl) -4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzimidyl) Phenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxy Benzamethylene)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide, (2,5,6-three Methyl benzhydryl)-2,4,4-trimethylpentylphosphine oxide, and the like.

As a particularly preferable one of the mercaptophosphine oxide photopolymerization initiators, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and 2,6-dimethoxybenzamide are mentioned. Mercapto diphenylphosphine oxide, 2,6-dichlorobenzhydryldiphenylphosphine oxide, 2,4,6-trimethylbenzimidylmethoxyphenylphosphine oxide, 2, 4,6-trimethylbenzimidylethoxyphenylphosphine oxide, 2,3,5,6-tetramethyl A monodecylphosphine oxide photopolymerization initiator such as a benzamidine diphenylphosphine oxide.

Further, in consideration of the storage stability of the die attach paste for a semiconductor of the present invention, especially a monothiol phosphine oxide photopolymerization initiator is preferable to an α-aminoalkylphenone photopolymerization initiator. Among them, the most preferred one of the monothiophosphine oxide photopolymerization initiators is 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Examples of the commercially available product of the α-aminoalkylphenone-based photopolymerization initiator include Irgacure 907, Irgacure 369, and Irgacure 379EG (all manufactured by BASF Corporation), and the like, as a monodecylphosphine oxide-based photopolymerization. Examples of the initiator include Lucilin TPO, DAROCUR TPO (all manufactured by BASF Corporation), and Micure TPO (manufactured by MIWON Co., Ltd.).

The amount of the photopolymerization initiator (4) used in the die attach paste for a semiconductor of the present invention is preferably 0.01 to 5 by mass based on 100 parts by mass of the compound (1) containing the (meth)acrylonitrile group. The range of the portion is more preferably 0.05 to 3 parts by mass, still more preferably 0.1 to 1 part by mass. When the amount of the photopolymerization initiator (4) is 0.01 parts by mass or more based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group, the crystal grain adhesion for semiconductor of the present invention can be appropriately exhibited. The paste is inhibited by the spread of the B-stage. In addition, when the amount of the photopolymerization initiator (4) is 5 parts by mass or less based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group, the semiconductor grain of the present invention can be used. The hardness of the B-stage compound of the adhesive is good, and it is not necessary to perform hot pressing on the grain formation.

Next, the thermal radical generating agent (5) will be described. heat The radical generating agent (5) is not particularly limited as long as it is a compound which generates a radical which contributes to radical polymerization initiation by heating.

Examples of the thermal radical generating agent (5) include an azo compound and an organic peroxide, and an organic peroxide is preferable. Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, dinonyl peroxide, peroxydicarbonate, and peroxyester. Among these, a one-minute half-life temperature of 120 ° C or more and 200 ° C or less is preferable. More preferably, it is a dialkyl peroxide or a peroxyester having a one-minute half-life temperature of 120 ° C or more and 200 ° C or less.

Commercial products of a dialkyl peroxide and a peroxy ester having a one-minute half-life temperature of 120 ° C or more and 200 ° C or less are, for example, Perocta O (manufactured by Nippon Oil Co., Ltd.) and Perbutyl O (Nippon Oil Co., Ltd.) Company system), Perhexa25Z (made by Nippon Oil Co., Ltd.), PercumylD (made by Nippon Oil Co., Ltd.), etc.

The amount of the thermal radical generator (5) used in the die attach paste for a semiconductor of the present invention is preferably 0.1 part by mass or more based on 100 parts by mass of the compound (1) containing the (meth)acrylonitrile group. The range of 10 parts by mass or less is more preferably 0.5 parts by mass or more and 6 parts by mass or less, still more preferably 1 part by mass or more and 3 parts by mass or less. When the amount of the thermal radical generating agent (5) is 0.1 part by mass or more based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group, the semiconductor die paste of the present invention can be used. The modulus of elasticity of the cured product is good. In addition, when the amount of the thermal radical generating agent (5) is 10 parts by mass or less based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group, the semiconductor die of the present invention is adhered. It is difficult to generate deflation during thermal hardening of the paste or during the manufacturing steps of the semiconductor package.

Next, the thermosetting accelerator (6) will be described. The thermosetting accelerator (6) is not particularly limited as long as it is a compound which promotes an oxirane ring structure or a propylene oxide ring structure and a reaction with a compound which reacts with the above.

Examples of the curing accelerator (6) include a block compound such as an alkylphosphine compound, an imidazole compound, an aliphatic amine, an alicyclic amine, a cyclic oxime, or a tetraphenylborate salt thereof, and a phenol. A compound of a hydroxyl group, a polyamine, a carboxylic acid anhydride, a dicyandiamide, an organic acid diterpene or the like.

From the viewpoint of the balance between the hardenability and the storage stability, an imidazole compound, a block compound thereof, and a block compound of a cyclic oxime are preferred. As an example of such a commercial product, Curezol 2E4MZ (made by Shikoku Chemical Industry Co., Ltd.), Curezol 2PZ-PW (made by Shikoku Chemical Industry Co., Ltd.), and Curezol 2P4MZ (made by Shikoku Chemical Industry Co., Ltd.) ), Curezol C11Z-CNS (manufactured by Shikoku Chemical Industry Co., Ltd.), U-CAT SA102 (manufactured by SANAPRO Co., Ltd.), U-CAT SA506 (manufactured by SANAPRO Co., Ltd.), U-CAT 5002 (manufactured by SANAPRO Co., Ltd.) )Wait.

The amount of use of the thermosetting accelerator (6) in the die attach paste for a semiconductor of the present invention is relative to a compound (2) containing a oxirane ring structure or a propylene oxide ring structure, and 100 parts by mass of the total of the (meth)acryl fluorenyl group-containing compound (8) contained in the same molecule, both of the methyl methacrylate group and the oxirane ring structure or the propylene oxide ring structure, It is preferably in the range of 0.5 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 6 parts by mass or less.

The amount of the thermosetting accelerator (6) used is relative to the compound (2) having a ring-containing structure including an oxirane ring structure or a propylene oxide ring structure, and a (meth) acrylonitrile group and ethylene oxide. When the ring structure or the propylene oxide ring structure contains 100 parts by mass of the total (meth) fluorenyl group-containing compound (8) in the same molecule, and 0.5 part by mass or more, the semiconductor of the present invention can be used. The modulus of elasticity of the hardened material of the die-adhesive paste becomes good. Further, the amount of the thermosetting accelerator (6) used is a compound (2) having a ring-containing structure containing an oxirane ring structure or a propylene oxide ring structure, and a (meth) acrylonitrile group and an epoxy group. When the both the ethane ring structure and the propylene oxide ring structure contain 100 parts by mass of the total (meth) fluorenyl group-containing compound (8) in the same molecule, and 10 parts by mass or less, the semiconductor of the present invention is used. It is difficult to generate deflation during thermal hardening of the die paste or during the manufacturing process of the semiconductor package.

Next, the filler (7) will be described.

Examples of the filler (7) include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, or alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, and calcium oxide. An inorganic filler such as magnesium oxide, aluminum oxide, aluminum nitride, crystalline cerium oxide, amorphous cerium oxide, boron nitride, titanium oxide, glass, iron oxide or ceramics, or an organic filler such as carbon or rubber-based filler Etc., including the kind, shape, and the like are not particularly limited. These may be used singly or in combination of two or more kinds as appropriate.

These fillers can be used separately for the purpose. Metal The filler is mainly added for the purpose of imparting conductivity to the die adhesion paste for the semiconductor, and the inorganic filler is mainly added for the purpose of imparting low thermal expansion property to the die adhesion paste for the semiconductor, and the organic filler is mainly used to impart adhesion to the semiconductor die. The stress relaxation property is added for the purpose, and in addition to this, various types of fillers may be added depending on various purposes such as thermal conductivity, low moisture absorption, and insulation.

The filler (7) preferably has an average particle diameter of 20 μm or less and a maximum particle diameter of 60 μm or less, more preferably an average particle diameter of 10 μm or less and a maximum particle diameter of 30 μm or less. When the average particle diameter is 20 μm or less and the maximum particle diameter is 60 μm or less, the storage stability and coating properties of the die attach paste for a semiconductor of the present invention are excellent.

The blending amount of the filler (7) is preferably 5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the total hardening component in the die attach paste for a semiconductor. When the blending amount of the filler (7) is 5 parts by mass or more, the elastic modulus of the cured product of the die bond for a semiconductor is good, and the control of thermal expansion and shrinkage is also easy. When the blending amount of the filler (7) is 80 parts by mass or less, the viscosity of the die attach paste for a semiconductor is appropriate.

In the die attach paste for a semiconductor of the present invention, it is preferred to add a polymerization inhibitor in order to increase storage stability, and thus a polymerization inhibitor may be added. The polymerization inhibitor is not particularly limited, but for example, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquihone, toluene, 2,5-di are suitably used. Ethoxyl-p-benzoquinone, 2,5-dihexanoic acid (caproic acid)-p-benzoquinone, 2,5-decyloxy-p-benzoquinone, p-tert-butyl phthalene Phenol, 2,5-di-tert-butyl hydroquinone, p-tert- Butyl catechol, mono-tert-butyl hydroquinone, 2,5-di-tert-pentyl hydroquinone, di-tert-butyl-p-cresol hydroquinone monomethyl Ether and phenothiazine. These may be used singly or in combination of two or more kinds as appropriate.

In general, the polymerization inhibitor is preferably added in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the compound (1) which is wholly contained in the (meth) acrylonitrile group.

The die attach paste for a semiconductor of the present invention may further contain a decane coupling agent (9) for the purpose of imparting adhesion to the support member.

The decane coupling agent (9) is an organic ruthenium compound having both a functional group reactively bonded to an organic material in the molecule and a functional group reactively bonded to the inorganic material, and generally has a structure as shown in the following formula 1. .

Here, examples of the functional group in which Y is reactively bonded to an organic material include a vinyl group, an epoxy group, an amine group, a substituted amine group, a (meth)acryl fluorenyl group, a fluorenyl group, and the like. Further, the functional group in which X is reactively bonded to the inorganic material is hydrolyzed by water or moisture to form a sterol group, and the sterol group is bonded to the inorganic material. Typical examples of X include an alkoxy group, an ethenyloxy group, a chlorine atom and the like. R ¹ is a divalent organic group, and R ² represents an alkyl group. i represents an integer from 1 to 3, and j represents an integer from 0 to 2. However, the sum of i and j is 3.

Among such decane coupling agents (9), the preferred one is Y and Compound (1) containing a (meth) acrylonitrile group and/or a compound (2) containing a oxirane ring structure or a propylene oxide ring structure and/or a maleic anhydride modified polyolefin (3) a compound having reactivity, preferably p-styryl trimethoxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl Triisopropoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3-propenyl methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-propenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropylmethyldimethoxydecane, 3-methyl Propylene methoxypropyl methyl dimethoxy decane, 3-propenyl methoxy propyl methyl diethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane 2- ( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidol Oxypropyl propyl triethyl Baseline, 3-glycidoxypropylmethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-amine Benzyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-Aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl Trimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane.

Further preferably, in the thermosetting reaction, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-glycidoxypropyltrimethoxy group which is easily incorporated into the hardened material Decane, 3-glycidoxypropylmethyldi Methoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, N-2-(aminoethyl)-3-amine Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltri Ethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) Propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane are preferred.

The amount of the decane coupling agent (9) is preferably in the range of 0.01% by mass or more and 8% by mass or less, more preferably 0.1% by mass or more and 5 parts by mass based on the total hardening component in the die attach paste for a semiconductor of the present invention. % below the range. When the total hardening component in the die attach paste for a semiconductor of the present invention is 0.01% by mass or more, the adhesion to the supporting member can be sufficiently exhibited. In addition, when the total hardening component in the die attach paste for a semiconductor of the present invention is 8% by mass or less, the storage stability can be improved regardless of the type of the decane coupling agent to be used.

The die attach paste for a semiconductor of the present invention preferably has a viscosity at 25 ° C of 50,000 mPa ‧ a or less. More preferably, the viscosity at 25 ° C is 25,000 mPa‧a or less. When the viscosity at 25 ° C is 50,000 mPa ‧ a or less, it is easy to apply the semiconductor die bond paste to the size of the crystal grains with good quantitative properties.

In the present invention, the shear viscosity of the die attach paste for a semiconductor is measured using a viscoelasticity measuring device. A representative condition for the viscosity measurement using a viscoelasticity measuring device will be described. A sample for adhering a semiconductor die to a viscoelasticity measuring device (manufactured by Anton-Paar Co., Ltd., type: MCR301) was used, and a cone-and-plate type mandrel of model CP-25 was used, with a temperature of 25.0 ° C and a shear rate of 10 s ^- The condition of ¹ determines the shear viscosity.

<Method of Manufacturing Semiconductor Package>

A method of manufacturing a semiconductor package using the die attach paste for a semiconductor of the present invention will be described. First, the die attach paste for a semiconductor of the present invention is applied to a crystal grain or a supporting member, and secondly, for example, ultraviolet rays are applied to a coated portion of the die attach paste for a semiconductor to form a compound containing (meth)acryl fluorenyl group (1). The photopolymerization is carried out, and the B-stage semiconductor die attach paste. Thereafter, thermal polymerization of crystal graining and thermosetting (compound (1) containing a (meth) acrylonitrile group or a compound (2) containing a ring structure having an oxirane ring structure or a propylene oxide ring structure is carried out. Further, by sealing, a semiconductor package having high reliability and high integration can be obtained. Still, it is also possible to perform thermal hardening and sealing at the same time.

The method of applying the die attach paste for a semiconductor is not particularly limited, and examples thereof include a dipping method, a brush coating method, a spray coating method, a wire coating method, a press method, a printing method, a jet dispensing method, an inkjet method, and the like. . The method of irradiating light such as ultraviolet rays to the application portion of the die attach paste for semiconductor is not particularly limited, but a flexible light guide tube is held by hand or mechanical operation and irradiated to a semiconductor die. A method of applying a coating portion of a paste, or a method of irradiating a crystal grain of a coated semiconductor die with a die or a support member on a conveyor belt, and irradiating it with a region irradiated with light such as ultraviolet rays. After the B-stage of the die attach paste for the semiconductor, after the grain is formed, The method of heat hardening is not particularly limited, and examples thereof include a method of putting in an oven, a method of placing a part after grain formation on a conveyor belt, and passing it to a region of a specific temperature.

In the method for producing a semiconductor package according to the present invention, a method of evaluating the grain shear strength at the time of grain formation and thermal hardening will be described. The evaluation of the grain shear strength is carried out, for example, according to specifications of MIL-STD-883G, IEC-60749-22, EIAJ-ED-4703, and the like. As a specific example, Dage-4000 (cut-off force tester, manufactured by Dage Co., Ltd.) was used, and the side faces of the joined crystal grains were pushed by a jig with a sensor to measure the joint required to break the bonding of the crystal grains and the support member. power. Further, in the case of bonding a wafer having a square of 2 mm square and a supporting member, the grain shear strength is preferably 58.8 N or more. If it is a bonding material or bonding method of 58.8N or more, the reliability of a semiconductor package can be made favorable.

<Semiconductor Package>

In the aspect of the invention, there is also a semiconductor package manufactured using the die attach paste for a semiconductor of the present invention. Examples of the semiconductor package include a Poin insertion type DO package, a TO package (Transistor Outline), a DIP (Dual Inline Package), a SIP (Single Inline Package), a ZIP (Zigzag Inline Package), and a PGA. (Pin Grid Array), SOP (Small Outline Package), SOJ (Small Outline J-leaded), CFP (Ceramic Flat Package), SOT (Small Outline Transistor), QFP (Quad Flat Package), PLCC ( Plastic Leaded Chip Carrier), BGA (Ball Grid Array), LGA (Land Grid Array), LLC (LeadLess Chip Carrier), TCP (Tape Carrier Package), LLP (Leadless Leadframe Package), DFN (Dual Flatpack No-leaded), COB (Chip On Board), and the like.

In the semiconductor package of the present invention, the die attaching paste for a semiconductor of the present invention is applied to a crystal grain or a supporting member, and secondly, a portion of the die attaching paste for a semiconductor is irradiated with, for example, ultraviolet rays for B-stage, and then crystallizing is performed. The particles are bonded to the heat and can be produced by sealing. The semiconductor package of the present invention manufactured in this manner is highly reliable.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples.

(Example 1)

10.3 g of bisphenol A olefin oxide adduct diacrylate (BP-4EAL manufactured by Kyoeisha Chemical Co., Ltd., compound name 2, 2'-bis[4-(propylene oxypolyethylene)) Phenyl]propane), 41.4 g of maleic anhydride modified polybutadiene (Ricon131MA17, manufactured by CRAYVALLEY, number average molecular weight 5400, anhydride equivalent 583), and 6.9 g of glycidyl methacrylate (BlemmerGH, manufactured by Nippon Oil Co., Ltd.) ), 10.3 g of hydrogenated bisphenol A type epoxy resin (YX-8000 manufactured by Mitsubishi Chemical Corporation), 0.1 g of 2,4,6-trimethylbenzhydryldiphenylphosphine oxide (DAROCUR manufactured by BASF Corporation) TPO), 0.3g dicumyl peroxide (Nippon Oil Co., Ltd. System Percumyl D), 0.7 g of diazabicycloundecene-tetraphenyl borate (U-CAT5002, manufactured by SANAPRO Co., Ltd.), 29.5 g of spherical cerium oxide gel (QS manufactured by Mitsubishi Rayon Co., Ltd.) -2), a rotating ‧ rpm mixer (THINKY Co., Ltd. foaming Taro ARE-310) was mixed and mixed to obtain a grain adhesion paste.

(Examples 2, 3 and Comparative Examples 1 to 3)

The same procedure as in Example 1 was carried out except that the types and amounts of the respective components were changed as shown in Table 1, to obtain a die attach paste.

In Table 1, SR-349 is an ethoxy group made by Sartomer. Bisphenol A diacrylate, FA-512M is a dicyclopentenyloxyethyl methacrylate manufactured by Hitachi Chemical Co., Ltd. Ricon131MA10 is a maleic anhydride modified polybutadiene (number average molecular weight 5000, acid anhydride equivalent 981) manufactured by CRAYVALLEY Co., Ltd., CTBN-1300X8 is a carboxy terminal acrylonitrile butadiene copolymer manufactured by Ube Industries, Ltd., EXA- 4850-150 is an epoxy resin (epoxy equivalent 450) manufactured by Dainippon Ink Chemical Industry Co., Ltd., PB-4700 is an epoxylated polybutadiene manufactured by Daicel Chemical Co., Ltd., Irgacure (registered trademark) 369 series 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 manufactured by BASF Corporation, DICY is dicyandiamide, KBM-403 is Shin-Etsu Co., Ltd. 3-Glycidoxypropyltrimethoxydecane manufactured by AEROSIL R972 is a hydrophobic cerium oxide filler surface-treated with dimethyldichloromethane manufactured by Nippon Aerosil Co., Ltd.

<Evaluation of Wet Spread Inhibition>

The suppression of wet spread of the die attach paste was evaluated by the following method.

The crystal grain was adhered to a crucible substrate and applied into a circular shape having a thickness of 200 μm and a diameter of 2 mm, and irradiated with ultraviolet rays of 1000 mJ/cm ² to be B-staged to obtain a test piece. Thereafter, the test piece was placed in an oven, and the temperature was raised to 170 ° C at a heating rate of 4 ° C / min, and then directly cured for 1 hour.

The grain adhesion paste on the test piece after hardening was observed under a microscope, and the diameter was measured, the rate of increase from the diameter at the time of coating was calculated, and the moisture spread suppression was evaluated by the increase rate of the diameter. The results are shown in Table 1. When the increase rate of the diameter was less than 5%, the wet spread inhibition was evaluated to be very good, and it was shown in Table 1 as ◎. Also, the increase rate of the diameter is 5% or more When the amount was less than 10%, the wet spread inhibition evaluation was good, and it was shown in Table 1 as ○ printing. Further, when the increase rate of the diameter was 10% or more, the evaluation of the wet spread suppression was poor, and it was shown in Table 1 as × printing.

<Evaluation of grain shear strength>

The grain shear strength was evaluated by the following method.

On a 5 mm square PPF lead frame (three layers of Ni, Pd, and Au plating on a Cu substrate), the die adhesion paste was applied in a square shape (thickness: 80 μm) of 2 mm on one side, and irradiated with 1000 mJ/ The cm ² ultraviolet light makes it B-staged. Further, using a die bonder MD-P200 (manufactured by Panasonic Co., Ltd.), a square-shaped tantalum wafer (thickness: 0.7 mm) of 2 mm was attached to the crystal grains at a temperature of 25 ° C, a load of 10 N, and a time of 1 second. Sticky on it. Thereafter, it was allowed to harden in an oven at 170 ° C for 1 hour.

The shear strength (N/wafer) at a temperature of 25 ° C in the obtained sample was measured using a shear adhesion tester Series 4000 (manufactured by Dage Co., Ltd.). The results are shown in Table 1. When the measured value of the shear strength was 58.8 N/wafer or more, the grain shear strength was evaluated as good, and it is shown in Table 1 as ○. Further, when the measured value of the shear strength was less than 58.8 N/wafer, the grain shear strength was evaluated as unsatisfactory, and it is shown as ×print in Table 1.

<Evaluation of preservation stability>

The storage stability of the die attach paste was evaluated by the following method. The die adhesion paste was allowed to stand at a temperature of 25 ° C for 3 days. Further, the shear viscosity of the die attach paste at the initial stage of standing and after 3 days was measured using a rotation mode of the viscoelasticity measuring device at a temperature of 25 ° C and a shear rate of 10 s ^-1 . The viscosity-increasing rate of the shear viscosity after standing for 3 days from the standstill was calculated, and the storage stability of the die-adhesive paste was evaluated by the viscosity-increasing rate. The results are shown in Table 1.

When the viscosity increase rate was less than 40%, the storage stability of the die attach paste was evaluated to be very good, and it was shown in Table 1 as ◎. Further, when the viscosity increase rate was 40% or more and less than 100%, the storage stability was evaluated as good, and in Table 1, it was shown as ○. Further, when the viscosity-increasing rate was 100% or more, the storage stability of the die attach paste was evaluated to be inferior, and it is shown in Table 1 as x-print.

From Table 1, it is judged that Examples 1 to 3 of the die attach paste for a semiconductor of the present invention suppress the wet spread by the B-stage, and have a high grain shear strength. Further, Example 1 using a mercaptophosphine oxide photopolymerization initiator (DAROCUR TPO) is an example 2 and 3 in which an alkylphenone photopolymerization initiator (Irgacure (registered trademark) 369) is used. Better storage stability.

Further, in Comparative Example 1 in which the conventional die bond for semiconductors was judged, when grain formation was performed at 25 ° C, the support member was not bonded, and the crystal grain shear strength was poor. Further, it was judged that Comparative Example 2 was not B-staged because it did not contain a photopolymerization initiator, and it was not possible to suppress wet spread. Further, it was judged that Comparative Example 3 did not contain the maleic anhydride-modified polyolefin, so that the hardness of the cured product was poor and the grain shear strength was poor. In other words, it is judged that the die attach paste for a semiconductor of the present invention suppresses wet propagation in a B-stage manner as compared with the conventional die attach paste for a semiconductor, and the crystal grain can be formed without heating, and Has a high degree of grain shear strength.

[Industrial availability]

The die attach paste for a semiconductor of the present invention can suppress the wet spread after coating by maintaining the coating property and the B-stage, and it is possible to increase the integration of the multi-die package. Moreover, since the film is adhered to the semiconductor package, the semiconductor die package of the die-bonded paste for semiconductor use of the present invention is highly integrated and highly reliable, even if it is not heated. Available for a variety of devices.

Claims (15)

A die attach paste for a semiconductor characterized by a compound (1) containing a (meth)acryl fluorenyl group, a compound having a ring structure containing an oxirane ring structure or a propylene oxide ring structure, and a horse The anhydride is modified with a polyolefin (3) and a photopolymerization initiator (4). The die attaching paste for a semiconductor according to claim 1, wherein the blending amount of the (meth)acrylonitrile group-containing compound (1) is 5% by mass or more and 80% by mass or less based on the total hardening component; The compounding amount of the compound (2) having a ring-containing structure of an oxirane ring structure or a propylene oxide ring structure is the total number of oxirane ring structures or propylene oxide ring structures relative to those derived from the aforementioned maleic anhydride. The ratio of the total number of the carboxylic anhydride structures of the maleic anhydride of the polyolefin (3) is 2.8 to 0.4; and the blending amount of the maleic anhydride-modified polyolefin (3) is 20% by mass based on the total hardening component. The amount of the photopolymerization initiator (4) blended is 0.01 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the compound (1) containing the (meth) acrylonitrile group. . The semiconductor die attach paste of claim 1 or claim 2 further comprising a thermal radical generating agent (5). The die attaching paste for a semiconductor according to claim 3, wherein the amount of the thermal radical generating agent (5) blended is 0.1 by mass based on 100 parts by mass of the compound (1) containing the (meth)acryl fluorenyl group. More than 10 parts by weight. The semiconductor die attach paste of claim 3 or claim 4, wherein the thermal radical generating agent (5) is an organic peroxide. The semiconductor die attaching paste according to claim 5, wherein the thermal radical generating agent (5) is a dialkyl peroxide or a peroxyester. The die attach paste for a semiconductor according to any one of claims 3 to 6, wherein the thermal radical generating agent (5) has a one-minute half-life temperature of 120 ° C or more and 200 ° C or less. The die attach paste for a semiconductor according to any one of claims 1 to 7, further comprising a thermosetting accelerator (6). The die attach paste for a semiconductor according to any one of claims 1 to 8, further comprising a filler (7). The die attach paste for a semiconductor according to any one of claims 1 to 9, wherein at least a part of the (meth)acryl fluorenyl group-containing compound (1) contains a plurality of (meth)acryl fluorenyl groups. A compound of a functional (meth) acrylonitrile group. The die attach paste for a semiconductor according to any one of claims 1 to 10, wherein at least a part of the (meth)acryloyl group-containing compound (1) is a (meth) acrylonitrile group and an epoxy group Both the alkane ring structure and the propylene oxide ring structure contain a (meth)acryl fluorenyl group-containing compound (8) in the same molecule. The die bond for a semiconductor according to any one of claims 1 to 11, wherein the maleic anhydride-modified polyolefin (3) is a copolymerized prepolymerized diene and a maleic anhydride. The die attach paste for a semiconductor according to any one of claims 1 to 12, wherein the maleic anhydride-modified polyolefin (3) has a number average molecular weight of more than 5,000. The die attach paste for a semiconductor according to any one of claims 1 to 13, wherein the photopolymerization initiator (4) is an alkylbenzene ketone photopolymerization initiator and a mercaptophosphine oxide photopolymerization. At least one of the initiators. A semiconductor package manufactured by using the die attach paste for a semiconductor according to any one of claims 1 to 14.