JP4894395B2 - Liquid resin composition and semiconductor device produced using liquid resin composition - Google Patents

Description

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

The problem of heat generated during the operation of semiconductor products has become more prominent with the increase in capacity, high-speed processing, and fine wiring of semiconductor products. So-called thermal management, which releases heat from semiconductor products, is an increasingly important issue. It has become to. For this reason, a method of attaching a heat radiating component such as a heat sink or a heat spreader to a semiconductor product is generally adopted, but a material having a higher thermal conductivity has been desired. Also, depending on the form of the semiconductor product, the semiconductor element itself may be bonded to a metal heat spreader, an organic substrate having a heat dissipation mechanism such as a thermal via, or the like, and a package using a metal lead frame. In this case, the back surface of the die pad (the part to which the semiconductor element is bonded) is exposed on the back surface of the package. In these cases, it is required that not only the thermal conductivity of the material to which the semiconductor element is bonded, but also good heat transfer at each interface, and it is necessary to eliminate factors that deteriorate thermal diffusion such as voids and peeling.
On the other hand, while lead elimination from semiconductor products is being promoted as part of environmental measures, lead-free solder is also used for mounting on the board, so the reflow temperature must be higher than that of tin-lead solder. . Since the reflow treatment at a high temperature increases the stress inside the package, peeling and cracks are likely to occur in the semiconductor product during reflow.
In addition, as for exterior plating of semiconductor products, the case of changing the lead frame plating to Ni—Pd for the purpose of lead removal is increasing. Here, Ni-Pd plating is thinly gold-plated (gold flash) for the purpose of improving the stability of the Pd layer on the surface. However, because of the smoothness of the Ni-Pd plating itself and the gold present on the surface, ordinary silver is used. Compared with a plated copper frame or the like, the adhesive strength is reduced. The decrease in adhesive force causes peeling and cracks in the semiconductor product during the reflow process.
As described above, a material excellent in adhesion to various interfaces and simultaneously having a low elastic modulus and excellent in low-stress properties is desired than a conventionally used die attach paste (see, for example, Patent Document 1). There was no.
JP 2000-273326 A

  The present invention relates to a liquid resin composition having a low viscosity, excellent workability, good adhesion (for example, Ni-Pd plating frame, etc.) and a low elastic modulus, and a die attach material for semiconductors or a heat dissipation member. It is to provide a semiconductor device excellent in reliability such as solder crack resistance and the like used as a bonding adhesive.

Such an object is achieved by the present invention described in the following [1] to [5].
[1] A liquid resin composition for adhering a semiconductor element or a heat dissipation member to a support, comprising (A) a filler, (B) a thermosetting resin, (C) a curing catalyst, and (D) an additive. The liquid resin composition, wherein the thermosetting resin (B) consists only of a compound having two of the same kind of functional groups in one molecule.
[2] The thermosetting resin (B) is a compound (B1) having two glycidyl groups in one molecule, a compound (B2) having two (meth) acryloyl groups in one molecule, and one molecule. The liquid resin composition according to [1], comprising a compound (B3) having two phenolic hydroxyl groups therein.
[3] The compound (B1) having two glycidyl groups in one molecule is represented by the compound (B11) having a polyalkylene oxide skeleton and a glycidyloxyphenyl group and the general formula (1) or the general formula (2). The liquid resin composition according to [2], comprising a compound (B12).

Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５は水素、メチル基、エチル基のいずれかであり、
Ｒ^３は、単結合又は炭素数１〜３の炭化水素基であり、
Ｇはグリシジル基である。

R ¹ , R ² , R ⁴ , and R ⁵ are any one of hydrogen, methyl group, and ethyl group,
R ³ is a single bond or a hydrocarbon group having 1 to 3 carbon atoms,
G is a glycidyl group.

Ｒ^６、Ｒ^７はそれぞれ水素又はアルキル基であり、ｎは１〜１０の整数、Ｇはグリシジル基である。

R ⁶ and R ⁷ are each hydrogen or an alkyl group, n is an integer of 1 to 10, and G is a glycidyl group.

[4] A semiconductor device manufactured using the liquid resin composition according to any one of [1] to [3] as a die attach material or a heat dissipation member bonding material.

  The liquid resin composition of the present invention is low in viscosity and excellent in workability, exhibits good adhesion with the Ni-Pd plating frame, and has low elastic modulus and good low stress properties. By using it as an adhesive for a touch material or a heat radiating member, it is possible to provide a highly reliable semiconductor device that has never been obtained.

The present invention is a liquid resin composition comprising a filler, a thermosetting resin, a curing catalyst, and an additive, the thermosetting resin comprising only a compound having two functional groups of the same type in one molecule, Excellent workability with viscosity, good adhesion to a support such as a Ni-Pd plating frame, and low elasticity and good low stress properties, so that a semiconductor element or a heat dissipation member is adhered to the support By using it as a liquid resin composition, it becomes possible to provide an unprecedented highly reliable semiconductor device. Here, the support is a lead frame, an organic substrate or the like in the case of bonding a semiconductor element, and a semiconductor element or a lead frame in the case of a heat dissipation member.
Hereinafter, the present invention will be described in detail.

  In the present invention, as filler (A), silver powder, gold powder, copper powder, aluminum powder, nickel powder, metal powder such as palladium powder, ceramic powder such as alumina powder, titania powder, aluminum nitride powder, boron nitride powder, Polymer powders such as polyethylene powder, polyacrylic acid ester powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, and polysiloxane powder can be used. Since the liquid resin composition may be discharged using a nozzle, the average particle size is preferably 30 μm or less in order to prevent nozzle clogging, and it is preferable that there are few ionic impurities such as sodium and chlorine. In particular, silver powder is preferably used when electrical conductivity and thermal conductivity are required. If it is the silver powder currently marketed for electronic materials normally, reduced powder, atomized powder, etc. can be obtained, and as an average particle diameter, an average particle diameter is 1 micrometer or more and 30 micrometers or less. Below this, the viscosity of the liquid resin composition becomes too high, and above this causes nozzle clogging during dispensing as described above, and silver powder other than for electronic materials may have a large amount of ionic impurities. So be careful. The shape is not particularly limited, such as flakes and spheres, but preferably flakes are used and are usually contained in the liquid resin composition in an amount of 70% by weight to 95% by weight. This is because when the proportion of silver powder is less than this, the conductivity deteriorates, and when it is more than this, the viscosity of the liquid resin composition becomes too high.

  The thermosetting resin (B) to be used in the present invention is a polymer that is heated together with the curing catalyst (C) to increase the molecular weight by heating, and 2 functional groups of the same type are contained in one molecule. It consists of only the compound which has. Here, a compound having two functional groups of the same type in one molecule means that if the compound is designed to have two functional groups at the time of compound preparation, a component having one function or more than three functions as impurities other than the target product. It may be included, and there is no problem unless a component having a monofunctional or trifunctional or higher function is intentionally added or a condition for generating a monofunctional or trifunctional or higher component is intentionally selected. Make it not exist. Here, the number of functional groups contained in one molecule is limited to two. However, when the number of functional groups is smaller than this, the cohesive force of the cured product is lowered and does not exhibit good adhesive properties. If the amount is larger than this, the crosslinking density becomes high, and as a result, the elastic modulus may be too high. Preferable functional groups contained in one molecule include glycidyl group, carboxy group, hydroxyl group, (meth) acryloyl group, (meth) allyl group, vinyl group, maleimide group, etc., for example, two glycidyl groups A compound having two functional groups other than the glycidyl group may be used in combination. More preferably used functional groups are a glycidyl group, a hydroxyl group, and a (meth) acryloyl group. The thermosetting resin (B) has a compound (B1) having two glycidyl groups in one molecule and (meth) in one molecule. It is particularly preferable to include a compound (B2) having two acryloyl groups and a compound (B3) having two phenolic hydroxyl groups in one molecule.

In the present invention, the compound (B1) having two glycidyl groups in one molecule is preferably used. This is because the cured product of the compound having a glycidyl group is particularly excellent in adhesiveness, and the functionalities contained in one molecule. The number of groups is limited to 2, but this is because when the number of functional groups is 1, the cohesive force of the cured product is reduced and good adhesiveness cannot be maintained. It may become too high and cause peeling from the support. The compound (B1) is not particularly limited as long as it has two glycidyl groups in one molecule. Among them, a compound (B11) having a polyalkylene oxide skeleton and a glycidyloxyphenyl group is preferable. . The compound (B11) is preferable because the elastic modulus of the cured product is low by introducing polyalkylene oxide into the molecular skeleton, that is, good low stress properties can be exhibited. For such purposes, the polyalkylene oxide skeleton is preferably one in which a linear or branched alkylene group having 2 to 6 carbon atoms is repeatedly bonded by an ether bond, and more preferably polyethylene oxide, polypropylene oxide, polybutylene. It is at least one selected from oxide and polytetramethylene oxide. When the number of carbons in the repeating unit is more than 6, crystallization is likely to occur, so that the effect of reducing the elastic modulus may not be expected.
As for the repeating number of a polyalkylene oxide, 2-50 are preferable. A more preferable repeating number is 2-10. This is because an alkylene glycol residue having a number of repetitions of 1 cannot be expected to have a low elastic modulus effect, and if it exceeds the upper limit, the viscosity of the liquid resin composition becomes too high and the curability deteriorates.

  The compound (B11) needs to have a glycidyloxyphenyl group, but this is low in reactivity with an aliphatic glycidyloxy group, and usable curing agents are limited to Lewis acids, acid anhydrides, and the like. It is because it ends up. By having a glycidyloxyphenyl group, a phenolic curing agent generally used in the field of electronic materials can be used.

  Such a compound (B11) can be obtained by a method as described in JP-A No. 2004-156024. That is, by obtaining a compound having ethylene oxide as a repeating unit and having a phenolic hydroxyl group at both ends by acetalization reaction of bisphenol A and triethylene glycol divinyl ether, and further reacting with epichlorohydrin, both ends are glycidyloxyphenyl groups. To obtain a compound having a polyalkylene oxide skeleton. Similarly, the polyalkylene oxide skeleton can be changed by selecting polypropylene oxide divinyl ether, polybutylene oxide divinyl ether, or polytetramethylene oxide divinyl ether as the divinyl ether to be used. Also, instead of bisphenol A, a bisphenol compound such as bisphenol F or biphenol or a derivative thereof, catechol, resorcinol, hydroquinone or a derivative thereof, a compound having two phenolic hydroxyl groups in one molecule such as naphthalenediol, anthracenediol, etc. Is possible.

As the compound (B1), it is preferable to use the compound (B11) and the compound (B12) in combination, but when only the compound (B11) is used, a cured product having a low elastic modulus and excellent in low stress is obtained. This is because the viscosity of the compound (B11) itself is high, and the resulting liquid resin composition also has a high viscosity and poor workability. When only the compound (B12) is used, Although it is possible to obtain a liquid resin composition having a low viscosity and excellent workability, the cured product has a low mechanical strength especially at a high temperature of 100 ° C. or higher.
As described above, since the compound (B11) has a high viscosity, it is desired to be used in combination with a low-viscosity compound. However, in addition to the use of the compound (B12), use of a solvent, a monofunctional epoxy compound, or the like is conceivable. Solvents are low-viscosity compounds such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, cyclohexanol, and γ-butyrolactone, and monofunctional epoxy compounds include phenyl glycidyl ether and cresyl glycidyl. A compound having one glycidyl group in one molecule such as ether.
However, the solvent must be volatilized during the curing reaction and cannot be used because it may cause voids in the cured product or remain in the cured product. This is because the voids in the cured product cause peeling during the reflow treatment, and the solvent remaining in the cured product causes deterioration of properties at the time of heating such as adhesiveness at high temperatures. On the other hand, when a monofunctional epoxy compound is used, problems such as voids do not occur because it is incorporated into the system during the curing reaction, but the cohesive strength of the cured product is reduced because the molecular weight of the cured product does not increase sufficiently, This is because, in particular, it causes a decrease in adhesive strength at a high temperature of 260 ° C., and this is more remarkable when a compound having a small functional group (high epoxy equivalent) with respect to the molecular weight is used, such as compound (B11). is there.

Therefore, in the present invention, the compound (B12) represented by the general formula (1) or the general formula (2) is used. These compounds (B12) have a low viscosity, are excellent in compatibility with the compound (B11), have two glycidyl groups in one molecule, and therefore do not reduce the cohesive force of the cured product, and further in the skeleton Since it has an alicyclic structure, it is effective for lowering the modulus of elasticity of the cured product. The compound (B12) preferably has few ionic impurities such as sodium and chlorine. Preferred examples of the compound represented by the general formula (1) include hydrogenated diglycidyl bisphenol A, hydrogenated diglycidyl bisphenol F, and substituted products thereof, which are commercially available for electronic materials. Examples of the compound shown in 2) include dimethylolcyclohexane diglycidyl ether.

  Here, since the compound (B11) has few functional groups with respect to the molecular weight (the epoxy equivalent is large), the reactivity of the compound (B12) tends to decrease because the glycidyl group is bonded to the aliphatic carbon atom. . Therefore, it is preferable to use a bisphenol type epoxy compound (B13) in combination for the purpose of maintaining good reactivity. The bisphenol type epoxy compound (B13) is a diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of biphenol, etc. It is a glycidyl etherified product.

  The compounding amounts of the compounds (B11), (B12), and (B13) are each preferably 15% by weight or more and 50% by weight or less with respect to the compound (B1). More preferably, the compounds (B11), (B12), and (B13) are each 20% by weight to 50% by weight, and particularly preferably 25% by weight to 45% by weight. This is because when the amount of the compound (B11) is less than this, the effect of lowering the elastic modulus is insufficient, and when it is more than this, the viscosity becomes too high. This is because when the amount of the compound (B12) is less than this, the viscosity becomes too high, and when it is more than this, the curability deteriorates. This is because if the amount of the compound (B13) is less than this, the curability becomes too bad, and if it is more than this, the elastic modulus becomes too high.

As the compound (B1), it is possible to use a compound having two glycidyl groups other than the compounds (B11), (B12), and (B13), but the viscosity, curability, and cured product of the liquid resin composition Considering the elastic modulus and the like, the content is preferably 30% by weight or less in the compound (B1), more preferably 20% by weight or less, and particularly preferably not included. As described above, monofunctional epoxy compounds cannot be used.
The compounding quantity of a compound (B1) is 30 to 85 weight% with respect to a thermosetting resin (B). A more preferable blending amount is 50% by weight or more and 75% by weight or less. If it is more or less than this, it is difficult to achieve both good adhesion and low elastic modulus.

  In the present invention, the compound (B2) having two (meth) acryloyl groups in one molecule is preferably used. This is because the compound (B2) has a low viscosity and has two functional groups of the same kind in the other molecule. This is because it is excellent in compatibility with the compound it has, and because it reacts quickly by using a reaction catalyst (reaction initiator) such as an organic peroxide. The number of functional groups contained in one molecule is limited to 2, but this is because when the number of functional groups is 1, the cohesive force of the cured product decreases and good adhesiveness cannot be maintained. In some cases, the elastic modulus of the cured product becomes too high and may cause separation from the support.

The compound (B2) is not particularly limited as long as it has two (meth) acryloyl groups in one molecule. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, zinc di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, polybutanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 10-decane Oruji (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate,
Cyclohexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, cyclohexanediethanoldi (meth) acrylate, cyclohexanedialkyl alcohol di (meth) acrylate, dimethanoltricyclodecane di (meth) acrylate, N, N'- Examples include methylene bis (meth) acrylamide, N, N′-ethylene bis (meth) acrylamide, and 1,2-di (meth) acrylamide ethylene glycol. Among them, preferable compound B2 is ethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 6- hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethanol tricyclodecane (meth) acrylate. The compounding quantity of a compound (B2) is 10 to 40 weight% with respect to a thermosetting resin (B). A more preferable blending amount is 15% by weight or more and 30% by weight or less. If it is less than this, there is no sufficient effect for reducing the viscosity of the liquid resin composition, and if it is more than this, it may cause a decrease in adhesiveness.

  In the present invention, the compound (B3) having two phenolic hydroxyl groups in one molecule is preferably used. This is a curing that is particularly excellent in moisture resistance by using the compound (B3) as a curing agent for the compound (B1). It is possible to obtain things. In the case of an alcoholic hydroxyl group in which the hydroxyl group is bonded to an aliphatic carbon atom, the reactivity with the compound (B1) is remarkably lowered. The number of functional groups contained in one molecule is limited to 2, but this is because when the number of functional groups is 1, the cohesive force of the cured product decreases and good adhesiveness cannot be maintained. In some cases, the elastic modulus of the cured product becomes too high and may cause separation from the support. The compound (B3) is not particularly limited as long as it has two phenolic hydroxyl groups in one molecule, but bisphenols such as bisphenol A, bisphenol F, and biphenol are particularly preferably used. The compounding quantity of a compound (B3) is 5 to 30 weight% with respect to a thermosetting resin (B). A more preferable blending amount is 8% by weight or more and 22% by weight or less. When it is less than this, the moisture resistance of the liquid resin composition is not sufficient, and when it is more than this, the adhesiveness may be lowered.

  The curing catalyst (C) used in the present invention is for accelerating the reaction of the thermosetting resin (B), and even if it is compounded in a large amount, even a compound that functions as a curing agent can be used as a curing agent. When the amount is small, it is handled as a curing catalyst. Specifically, it is a compound that is blended in a small amount of less than 5% by weight with respect to the thermosetting resin (B) and accelerates the reaction of the thermosetting resin (B), and includes a compound usually called an initiator.

  The curing catalyst (C) preferably used includes an adduct of 2-methylimidazole and 2,4-diamino-6-vinyltriazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, dicyandiamide, or an organic catalyst. An oxide is mentioned. It is also possible to use phosphorus compounds, amine compounds other than the above, and the like. As the organic peroxide, those having a decomposition temperature of 40 to 140 ° C. in a rapid heating test (decomposition start temperature when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min) are preferable. If the decomposition temperature is less than 40 ° C., the storage stability of the liquid resin composition at normal temperature is deteriorated, and if it exceeds 140 ° C., the curing time becomes extremely long.

Specific examples include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis. (T-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy)
Cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (t-butyl) Peroxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl Oxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, Cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2 -Ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α '-Bis Neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecane Noate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t -Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhe Sanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Isopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t- Butyl peroxy-m-toluoyl benzoate, t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, t-butyl peroxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t -Butylperoxycarbonyl) benzophenone, etc. And the like. Here, since the liquid resin composition of the present invention is usually used under illumination such as a fluorescent lamp, if a photopolymerization initiator is contained, an increase in viscosity is observed due to reaction during use. It is not preferable to contain an initiator. “Substantially” means that a small amount of the photopolymerization initiator may be present to such an extent that no increase in viscosity is observed, and it is preferably not contained.
The compounding quantity of a curing catalyst (C) is less than 5 weight% with respect to a thermosetting resin (B). It is because the elasticity modulus of hardened | cured material will become high too much when it exceeds this.

The additive (D) used in the present invention is a coupling agent, an antifoaming agent, a surfactant and the like, and is substantially free of a solvent and a monofunctional reactive diluent used for the purpose of reducing the viscosity. “Substantially not contained” means that, for example, even if a solvent is contained in various additives, the amount thereof is 1% by weight or less based on the thermosetting resin (B) + curing catalyst (C) + additive (D). Yes, more preferably 0.5% by weight or less, and particularly preferably not included.
As a preferable coupling agent, a compound having two trialkoxysilyl groups in one molecule can be given. Of these, preferred are those having a sulfide bond. Such compounds include bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (tributoxysilylpropyl) tetrasulfide, bis (dimethoxymethylsilylpropyl) tetrasulfide, bis (diethoxy Methylsilylpropyl) tetrasulfide, bis (dibutoxymethylsilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) disulfide, bis (dimethoxymethylsilyl) Propyl) disulfide, bis (diethoxymethylsilylpropyl) disulfide, bis (dibutoxymethylsilylpropyl) disulfide and the like.

  The liquid resin composition of the present invention can be produced, for example, by premixing each component, kneading using three rolls, and degassing under vacuum.

  A known method can be used as a method of manufacturing a semiconductor device using the liquid resin composition of the present invention. For example, using a commercially available die bonder, the liquid resin composition is dispensed on a predetermined portion of the lead frame, and then the chip is mounted and heat-cured. Then, a semiconductor device is manufactured by wire bonding and transfer molding using an epoxy resin. Alternatively, after the flip chip bonding, a liquid resin composition is dispensed on the back surface of a chip such as a flip chip BGA sealed with an underfill material, and a heat radiating component such as a heat spreader or lid is mounted and cured.

[Example 1]
The filler (A) is flaky silver powder (hereinafter referred to as silver powder) having an average particle diameter of 8 μm and a maximum particle diameter of 30 μm, and a diglycidyl etherified product of a reaction product of polyalkylene oxide divinyl ether and bisphenol A as a thermosetting resin (B). (EXA-4850-1000, manufactured by Dainippon Ink and Chemicals, Inc., compound (B1) having two glycidyl groups in one molecule, hereinafter referred to as compound B111), hydrogenated bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. ), YX-8000, epoxy equivalent 205, R ¹ , R ² , R ⁴ and R ^{5 in} the general formula (1) are —H, R ³ is —C (CH ₃ ) ₂ —, and a glycidyl group in one molecule. Compound (B1) having two of these, hereinafter referred to as compound B121), diglycidyl bisphenol obtained by reaction of bisphenol A with epichlorohydrin A (epoxy equivalent 180, liquid at room temperature, compound (B1) having two glycidyl groups in one molecule, hereinafter compound B13), ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester EG, one molecule) Compound (B2) having two (meth) acryloyl groups therein, hereinafter referred to as compound B21), bisphenol F (Dainippon Ink and Chemicals, DIC-BPF, hydroxyl equivalent 100, 2 phenolic hydroxyl groups in one molecule One compound (B3), hereinafter referred to as Compound B3), dicyandiamide (hereinafter referred to as Compound C1), 2-phenyl-4-methyl-5-hydroxymethylimidazole (Cureazole 2P4MHZ: Shikoku Kasei Kogyo Co., Ltd.) as curing catalyst (C) Compound C2), dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, rapid heating Decomposition temperature in the experiment: 126 ° C., hereinafter referred to as compound C4), bis (triethoxysilylpropyl) tetrasulfide (manufactured by Nippon Unicar Co., Ltd., A-1289) as additive (D), triethoxysilyl group in one molecule Two compounds and a compound having a sulfide bond, hereinafter compound D1) are blended as shown in Table 1, and a liquid resin composition is obtained by kneading and defoaming using three rolls, and evaluated by the following evaluation method. The results are shown in Table 1. In addition, a mixture ratio is a weight part.

[Examples 2 to 6]
Evaluation was performed after blending at the ratio shown in Table 1 and obtaining a liquid resin composition in the same manner as in Example 1. In Example 2, 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1, 6HX, compound (B2) having two (meth) acryloyl groups in one molecule, hereinafter compound B22) In Example 3, a diglycidyl etherified product of a reaction product of polyalkylene oxide divinyl ether and bisphenol A (EXA-4850-150, manufactured by Dainippon Ink & Chemicals, Inc., compound having two glycidyl groups in one molecule) (B1), hereinafter referred to as Compound B112), in Example 4, dimethylolcyclohexane diglycidyl ether (manufactured by Tohto Kasei Co., Ltd., ZX-1658, epoxy equivalent 130-140, R ⁶ , R ^{7 in} the general formula (2) is A compound (B1) in which H and n are 1 and two glycidyl groups in one molecule, hereinafter referred to as Compound B122) In adduct of 2-methylimidazole and 2,4-diamino-6-vinyl-triazine (Curezol 2MZ-A: Shikoku Chemicals Co., Ltd., hereinafter Compound C3) were used.

[Comparative Examples 1-5]
Evaluation was performed after blending at the ratio shown in Table 1 and obtaining a liquid resin composition in the same manner as in Example 1. In Comparative Examples 1 and 2, lauroyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester L, a compound having one (meth) acryloyl group in the molecule, hereinafter referred to as compound E21), and in Comparative Example 3, orthocresol novolak. Glycidyl ether (softening point 70 ° C., epoxy equivalent 210, compound having three or more glycidyl groups in one molecule, hereinafter referred to as compound E11), Comparative Example 4 was cresyl glycidyl ether (epoxy equivalent 185, glycidyl in one molecule). A compound having one group, hereinafter referred to as compound E12), trimethylolpropane trimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester TMP), a compound having three (meth) acryloyl groups in the molecule, in Comparative Example 5, Compound E22) was used.

Evaluation method / storability (viscosity change rate): Using an E-type viscometer (3 ° cone), the value at 25 ° C. and 2.5 rpm was measured immediately after the production of the liquid resin composition. A viscosity value of 20 ± 10 Pa · S was accepted. The unit of viscosity is Pa · S.
Adhesive strength: Using a liquid resin composition shown in Table 1, a 6 × 6 mm silicon chip was mounted on a Ni-Pd frame flashed with gold and cured in a 150 ° C. oven for 30 minutes. After curing and after moisture absorption (85 ° C., 85%, 72 hours), the hot die shear strength at 260 ° C. was measured using an automatic adhesive force measuring apparatus. The case where the die shear strength when heated at 260 ° C. was 40 N / chip or more was regarded as acceptable. The unit of adhesive strength is N / chip.
Elastic modulus: 4 × 20 × 0.1 mm film-shaped test pieces were prepared using the liquid resin composition shown in Table 1 (curing conditions: 150 ° C. for 30 minutes), and the dynamic viscoelasticity measuring machine (DMA) was used. The measurement was performed in the pull mode. The measurement conditions are as follows.
Measurement temperature: room temperature to 300 ° C
Temperature increase rate: 5 ° C / min Frequency: 10Hz
Load: 100mN
The storage elastic modulus at 250 ° C. was regarded as the elastic modulus, and the case of 200 MPa or less was accepted. The unit of elastic modulus is MPa.

Reflow resistance: Using the liquid resin composition shown in Table 1, the following substrate (lead frame) and silicon chip were cured and bonded at 150 ° C. for 30 minutes. The die-bonded lead frame is sealed with a sealing material (Sumicon EME-7026, manufactured by Sumitomo Bakelite Co., Ltd.) to form a semiconductor device (package), and moisture absorption treatment is performed at 60 ° C. and a relative humidity of 60% for 192 hours, followed by IR reflow. Treatment (260 ° C., 10 seconds, 3 reflows) was performed. The degree of peeling of the treated package was measured with an ultrasonic flaw detector (transmission type). The case where the peeling area of the die attach part was less than 10% was regarded as acceptable. The unit of peeling area is%.
Package: QFP (14 x 20 x 2.0 mm)
Lead frame: Ni-Pd frame flashed with gold Chip size: 6 x 6 mm
Liquid resin composition curing conditions: 150 ° C. in oven for 15 minutes

The liquid resin composition of the present invention has a low viscosity and excellent workability, exhibits a good adhesive force with the Ni-Pd plating frame, and has a low elastic modulus and excellent low stress properties. It can be used suitably for a highly reliable semiconductor device that has never been used.

Claims (3)

  A liquid resin composition for adhering a semiconductor element or a heat dissipation member to a support, comprising (A) a filler, (B) a thermosetting resin, (C) a curing catalyst, and (D) an additive, The curable resin (B) is composed of only a compound having two functional groups of the same kind in one molecule, and a compound (B1) having two glycidyl groups in one molecule, and (meth) acryloyl in one molecule. A compound (B2) having two groups and a compound (B3) having two phenolic hydroxyl groups in one molecule, and the filler (A) is 70% by weight or more in the liquid resin composition, A liquid resin composition comprising 95% by weight or less. The compound (B1) having two glycidyl groups in one molecule is a compound (B11) having a polyalkylene oxide skeleton and a glycidyloxyphenyl group and a compound (B12) represented by the general formula (1) or the general formula (2). ) and liquid resin composition according to claim 1, characterized in that it comprises a.

R ¹ , R ² , R ⁴ , and R ⁵ are any one of hydrogen, methyl group, and ethyl group,
R ³ is a single bond or a hydrocarbon group having 1 to 3 carbon atoms,
G is a glycidyl group.

R ⁶ and R ⁷ are each hydrogen or an alkyl group, n is an integer of 1 to 10, and G is a glycidyl group. A semiconductor device manufactured by using the liquid resin composition according to claim 1 as a die attach material or a heat radiation member bonding material.