JP2014074132A - Thermosetting resin composition for semiconductor bonding and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition for semiconductor bonding, which has high thermal conductivity and excellent heat dissipation properties and is capable of satisfactorily joining a semiconductor element to a metal substrate.SOLUTION: The thermosetting resin composition for semiconductor bonding contains, as essential components: (A) a (meth)acrylic ester compound or a (meth)acrylamide compound which has a hydroxyl group; (B) a radical initiator; (C) fine silver particles having an average particle diameter of 10-100 nm, which are provided with a coating layer of an organic compound on their surfaces or are dispersed in an organic compound; (D) a silver powder having an average particle diameter of 0.5-30 μm; and (E) a solvent. A semiconductor device is manufactured using the thermosetting resin composition.

Description

  The present invention relates to a thermosetting resin composition for semiconductor bonding and a semiconductor device, which are excellent in high thermal conductivity and heat dissipation, and can satisfactorily bond a semiconductor element to a metal substrate.

  Generally, a semiconductor device is manufactured by bonding a semiconductor element such as a semiconductor chip to a lead frame with a die bonding material. Conventionally, Au-Si eutectic, solder, conductive adhesive, and the like are known as semiconductor die bonding materials, but in recent years, conductive adhesives have been widely used in terms of workability and cost. .

  Semiconductor elements such as semiconductor chips tend to have higher integration density and higher heat generation per unit area with higher integration and miniaturization. Therefore, in a semiconductor device on which a semiconductor element is mounted, it is necessary to efficiently dissipate the heat generated from the semiconductor element to the outside, and improvement of the thermal conductivity of the die bonding material is a problem.

  In addition, solder bonding is the mainstream for element bonding of power device packages. However, due to environmental issues, solder is becoming increasingly deleaded. Accordingly, in mounting applications and die bonding applications, high heat conduction instead of solder is used. The demand for paste is increasing.

  However, the conventional conductive paste has a smaller thermal conductivity than that of solder, and further higher thermal conductivity is desired.

  On the other hand, if many inorganic fillers such as silver powder are added in order to improve the thermal conductivity of the conductive paste, the viscosity will increase and the coating workability will decrease, or the cured product will be brittle and the adhesive strength between the lead frame and the device There is a problem that becomes low.

  In order to solve these problems, attention has recently been focused on a bonding method using silver nanoparticles, which enables bonding under conditions lower than that of bulk silver. However, since pressurization and heating are usually required at the time of bonding, the problems are that damage to the element can be considered and general versatility is poor due to problems on the apparatus.

  In such a flow, in addition to a method in which dicarboxylic acid is added to silver nanoparticles and bonded without pressure (see Patent Document 1), die bonding in which silver nanoparticles and micrometer-sized silver powder are mixed with thermosetting resin A paste (see Patent Document 2) has been proposed.

JP2011-240406 Japanese Patent No. 4828178

  However, although the bonding material described in Patent Document 1 is excellent in specific resistance, it is limited to bonding to a metal substrate and does not adhere to a silicon chip that has not been subjected to metal plating. In addition, the die bond paste described in Patent Document 2 has low adhesiveness with copper and high thermal conductivity that can be used as an alternative material for solder.

  Therefore, the present invention has been made to solve the above-described problems, and is excellent in high thermal conductivity and heat dissipation, can satisfactorily join a semiconductor element to a metal substrate, and has connection reliability with respect to a temperature cycle after mounting. An object of the present invention is to provide a thermosetting resin composition for a semiconductor that can be improved and a semiconductor device using the same.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have excellent thermal conductivity and heat dissipation, can satisfactorily join a semiconductor element to a metal substrate, and have reliable connection to a temperature cycle after mounting. Provided are a thermosetting resin composition for a semiconductor capable of improving the properties and a semiconductor device using the same.

  That is, the semiconductor thermosetting resin composition of the present invention comprises (A) a hydroxyl group-containing (meth) acrylic acid ester compound or (meth) acrylamide compound, (B) a radical initiator, and (C) a surface. A silver fine particle having an average particle size of 10 to 100 nm, provided with a coating layer of organic compound or dispersed in an organic compound, (D) a silver powder having an average particle size of 0.5 to 30 μm, and (E) Solvent is an essential component.

  The semiconductor device of the present invention is characterized in that a semiconductor element is bonded onto a semiconductor element support member using the semiconductor thermosetting resin composition of the present invention.

  Since the thermosetting resin composition for semiconductor bonding of the present invention has high thermal conductivity, it is excellent in heat dissipation and can satisfactorily bond a semiconductor element to a metal substrate.

  In addition, the semiconductor device of the present invention is formed by bonding a semiconductor element on a semiconductor element support member using the resin composition as described above, and the connection reliability with respect to the temperature cycle after mounting is dramatically higher than before. It will be improved.

  First, the thermosetting resin composition for semiconductor bonding of the present invention will be described. This resin composition has the above-described components as essential components, and each component will be described below.

  The (A) hydroxyl group-containing (meth) acrylic acid ester compound or (meth) acrylamide compound used in the present invention is a (meth) acrylic acid ester compound having one or more (meth) acrylic groups in one molecule. Or it is a (meth) acrylamide compound and contains a hydroxyl group. By containing a hydroxyl group, the sinterability by the reduction effect is promoted and the adhesiveness is improved.

  The hydroxyl group is an alcoholic group in which a hydrogen atom of an aliphatic hydrocarbon group is substituted. The hydroxyl group content is preferably 1 to 50 per molecule, and the hydroxyl group content is If it is within the range, there is no inhibition of sinterability due to excessive curing, which is preferable.

  Examples of such compounds include compounds represented by the following general formulas (I) to (IV).

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は炭素数１〜１００の２価の脂肪族炭化水素基又は環状構造を持つ脂肪族炭化水素基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic hydrocarbon group having 1 to 100 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure.)

（式中、Ｒ^１及びＲ^２はそれぞれ上記と同じものを表す。）

(In the formula, R ¹ and R ² are the same as described above.)

（式中、Ｒ^１は上記と同じものを表し、ｎは１〜５０の整数を表す。）

(Wherein, ^{R 1} represents the same as above, n is an integer of 1 to 50.)

（式中、Ｒ^１及びｎはそれぞれ上記と同じものを表す。）

(Wherein R ¹ and n each represent the same as above)

As the (meth) acrylic acid ester compound or (meth) acrylamide compound as the component (A), the above-mentioned compounds can be used alone or in combination of two or more. In general formulas (I) and (II), the carbon number of R ² is preferably 1 to 100, more preferably 1 to 36, and the carbon number of R ² is in such a range. This is preferable because there is no inhibition of sinterability due to excessive curing.

  (A) As for the compounding quantity of a component, 1-20 mass parts is preferable with respect to 100 mass parts of total amounts of the silver fine particle and silver powder mentioned later. If this blending amount is less than 1 part by mass, the adhesive strength tends to decrease, and if it exceeds 20 parts by mass, the resin content in the cured product layer increases, and the specific resistance and thermal conductivity characteristics tend to decrease. There is. By setting it as such a blending range, it is possible to easily prevent the silver particles from contacting each other and to maintain the mechanical strength of the entire adhesive layer by utilizing the adhesive performance of the acrylic resin.

  As the radical initiator (B) used in the present invention, a catalyst usually used for radical polymerization can be used, and is not particularly limited. However, a rapid heating test (1 g of a sample is placed on an electric heating plate). It is desirable that the decomposition temperature is 40 to 140 ° C. in the measurement test of the decomposition start temperature when the temperature is raised at 4 ° C./min. If this decomposition temperature is less than 40 ° C., the storage stability of the die attach paste at room temperature will deteriorate, and if it exceeds 140 ° C., the curing time may become extremely long. In addition, the temperature at the time of 1% mass reduction | decrease with respect to the mass before a sample is heated here is set as decomposition start temperature.

  Examples of the radical initiator whose decomposition initiation temperature satisfies the above conditions include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxyneodecanoate, dicumyl peroxide, and the like. Is mentioned.

  This (B) radical initiator may be used alone or in admixture of two or more in order to control curability. Furthermore, various polymerization inhibitors can be added in advance in order to improve the storage stability of the die attach paste.

  As for the compounding quantity of this (B) radical initiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of (A) component. If the amount exceeds 10 parts by mass, the change in the viscosity of the die attach paste may increase with time, which may cause a problem in workability.

  The silver fine particles (C) used in the present invention are those in which a coating layer of an organic compound is provided on the metal surface of silver fine particles having an average particle diameter of 10 to 100 nm, or the silver fine particles are dispersed in the organic compound. It is something to be made. Here, the average particle diameter other than the spherical particles indicates the short side. In such a form, since the silver fine particles contained can be prevented from directly contacting the metal surface, the formation of agglomerates of silver fine particles can be suppressed, and the silver fine particles are dispersed individually Can be retained. In addition, this average particle diameter is measured by TEM or SEM.

The organic compound provided on the surface of the silver fine particles or for dispersing the silver fine particles includes an organic compound having a molecular weight of 20000 or less as a constituent element, specifically, a functional group such as an amino group or a carboxyl group. Organic compounds are used.
Examples of the organic compound containing a carboxyl group used herein include one or more organic compounds selected from organic carboxylic acids having a molecular weight of 110 to 20000, such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, eicosanoic acid, docosanoic acid, 2-ethylhexanoic acid, oleic acid, linoleic acid, linolenic acid, and terminal dipropionic acid polyethylene oxide. Furthermore, as the organic compound, a carboxylic acid derivative of the carboxylic acid described above can also be used.
Examples of the organic compound containing an amino group used herein include alkylamines and the like, for example, butylamine, methoxyethylamine, 2-ethoxyethylamine, hexylamine, octylamine, 3-butoxypropylamine, nonylamine, dodecyl. Primary amines such as amine, hexadodecylamine, octadecylamine, cocoamine, tallowamine, tallowamine hydroxide, oleylamine, laurylamine, stearylamine, 3-aminopropyltriethoxysilane, dicocoamine, dihydrogenated tallowamine, and Secondary amines such as distearylamine and the like, as well as dodecyldimethylamine, didodecylmonomethylamine, tetradecyldimethylamine, octadecyldimethylamine, cocodimethylamine, Tertiary amines such as decyltetradecyldimethylamine and trioctylamine, as well as naphthalenediamine, stearylpropylenediamine, octamethylenediamine, nonanediamine, terminal diamine polyethylene oxide, triamine terminal polypropylene oxide, diamine terminal polypropylene oxide There are diamines such as.

  If the molecular weight of the organic compound that covers or disperses the metal particles is greater than 20000, the organic compound is less likely to be detached from the surface of the metal particles, and the organic compound may remain in the cured product after firing the paste. And as a result, a decrease in conductivity may occur. Therefore, from the viewpoint, it is preferable that the molecular weight of the organic compound covering the surface is small. Further, the molecular weight is preferably 50 or more, and if the molecular weight is less than 50, the storage stability of silver particles is inferior, which is not preferable.

  The silver fine particles preferably have a mass ratio of 90:10 to 99.5: 0.5 between the silver fine particles and the organic compound that coats or disperses the silver fine particles. At this time, if the amount of the organic compound is small relative to the silver fine particles, the suppression of aggregation becomes insufficient, and if the amount is large, the organic compound may remain in the cured product after firing. Since a reduction may occur, it is not preferable.

  The (D) silver powder used in the present invention is a silver powder having an average particle diameter of 0.2 to 30 μm, and may be silver powder as an inorganic filler that is usually added to impart conductivity to the resin adhesive. That's fine. The bonding strength between the semiconductor element and the support substrate can be further improved by adding micron-order silver particles such as (D) silver powder in addition to the silver fine particles of the component (C). Moreover, as a shape of the silver particle used here, things, such as flake shape, scale shape, resin shape, rod shape, wire shape, spherical shape, plate shape, are mentioned, for example. The average particle diameter is calculated by a laser diffraction method.

  Here, the silver fine particles of the component (C) and the silver powder of the component (D) are, as described above, such that when the total amount is 100 parts by mass, the component (A) is 1 to 20 parts by mass. Blended. When the component (A) is less than 1 part by mass, the silver component is too much, the viscosity is too high and the handling is difficult and unpreferable as an adhesive. Ensuring conductivity is insufficient, and heat dissipation is reduced.

  In addition, the ratio of these (C) component and (D) component is the mass ratio of (C) component: (D) component 10: 90-90: 10 when these total amounts are 100 mass parts. It is preferable. When the amount of the component (C) is too small relative to the component (D), it is difficult to ensure high thermal conductivity. There is a possibility that workability may be deteriorated due to a thread pulling phenomenon at the time of mounting.

  As the solvent (E) used in the present invention, a known solvent can be used as long as it functions as a reducing agent. As this solvent, alcohol is preferable, and examples thereof include aliphatic polyhydric alcohols. Examples of the aliphatic polyhydric alcohol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, and polyethylene glycol. These solvents can be used alone or in combination of two or more.

  The silver oxide and metal substrate partially present in the silver powder and silver nanoparticles, because the alcohol solvent that functions as a reducing agent is heated to a high temperature by heat treatment during paste curing (sintering), thereby increasing the alcohol reducing power. It is considered that the upper metal oxide (for example, copper oxide) is reduced by alcohol to be a pure metal, and as a result, a hardened film having higher density and higher conductivity and high adhesion to the substrate can be formed. In addition, by being sandwiched between the semiconductor element and the metal substrate, the alcohol is partially refluxed during the heat treatment during paste curing, and the alcohol that is the solvent is not lost from the system due to volatilization. With temperature, the metal oxide is reduced more efficiently.

  Specifically, the solvent has a boiling point of 100 to 300 ° C, preferably 150 to 290 ° C. If the boiling point is less than 100 ° C., the volatility is high even at room temperature, so that the reduction ability is easily reduced due to volatilization of the dispersion medium, and stable adhesive strength cannot be obtained. On the other hand, if the boiling point exceeds 300 ° C., it is difficult to sinter the conductive film, it lacks denseness, and does not volatilize, leaving the solvent in the film, which is not preferable.

  The amount of the (E) solvent is preferably 7 to 20 parts by mass when the total amount of the component (C) and the component (D) is 100 parts by mass. If the amount is less than 7 parts by mass, the viscosity may be increased and workability may be reduced. If the amount exceeds 20 parts by mass, the viscosity may be reduced, and silver settling and reliability in the paste may be reduced.

  In the thermosetting resin composition for semiconductor adhesion of the present invention, in addition to the above components, a curing accelerator, rubber or silicone generally blended in this type of composition as long as the effects of the present invention are not impaired. A low stress agent such as a coupling agent, an antifoaming agent, a surfactant, a colorant (pigment, dye), and other various additives can be blended as necessary. Each of these additives may be used alone or in combination of two or more.

  The thermosetting resin composition for semiconductor bonding according to the present invention is prepared by thoroughly mixing the components (A) to (E) described above and additives such as a coupling agent blended as necessary. It can be prepared by performing a kneading process using a Perth, a kneader, a three-roll mill or the like and then defoaming.

  The thermosetting resin composition for semiconductor bonding of the present invention is excellent in high thermal conductivity and heat dissipation, and can favorably bond a semiconductor element to a metal substrate.

  Next, the semiconductor device of the present invention will be described.

  The semiconductor device of the present invention is obtained by bonding a semiconductor element onto a semiconductor element support member using the above-described thermosetting resin composition for bonding semiconductors.

  Here, the semiconductor element may be a known semiconductor element, and examples thereof include a transistor and a diode. Examples of the semiconductor element support member include copper, silver-plated copper, and PPF (preplating lead frame). By using the thermosetting resin composition for semiconductor bonding of the present invention, metal substrates can be bonded to each other without pressure, and semiconductor elements not subjected to metal plating can also be bonded. Further, when a solvent functioning as a reducing agent such as alcohol is used as the solvent, sufficient bonding with the base metal copper is possible. In the semiconductor device thus obtained, the connection reliability with respect to the temperature cycle after mounting the semiconductor element is drastically improved as compared with the prior art.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.

(Examples 1-3, Comparative Examples 1-5)
Each component was mixed according to the composition in Table 1 and kneaded with a roll to obtain a resin paste for semiconductors. The obtained resin paste for semiconductor was evaluated by the following method. The results are shown in Table 1. In addition, the material as used in the Example and the comparative example used the commercial item as follows.

(A-1): Hydroxylethylacrylamide (manufactured by Kojin Co., Ltd., HEAA)
(A-2): Glycerin polydiglycidyl ether diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 80MFA)
(CA-1): 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester 1, 6HX)

(B): Dicumyl peroxide (manufactured by NOF Corporation, trade name: Park Mill D, decomposition temperature in rapid heating test: 126 ° C.)
(C): Silver fine particles (manufactured by Mitsuboshi Belting Ltd., trade name: MDot, average particle size: 50 nm)
(D): Silver powder (made by Fukuda Metal Foil Industry Co., Ltd., trade name: AgC-212D, average particle diameter: 5 μm)

(E-1): Diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.)
(CE-1): Butyl carbitol acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation method>
[viscosity]
The value at 25 ° C. and 5 rpm was measured using an E-type viscometer (3 ° cone).
[Pot life]
The number of days until the viscosity when the semiconductor resin paste was left in a constant temperature bath at 25 ° C. increased 1.5 times or more of the initial viscosity was measured.

[Adhesive strength]
Mount a 4mm x 4mm silicon chip and a backside gold chip with a gold deposition layer on the bonding surface on a solid copper frame and PPF (Ni-Pd / Au plated copper frame) using a semiconductor resin paste, Cured at 200 ° C. for 60 minutes. After curing and moisture absorption treatment (85 ° C., relative humidity 85%, 72 hours), the hot die shear strength at 260 ° C. was measured using a mount strength measuring device.

[Thermal conductivity]
According to JIS R1611-1997, the thermal conductivity of the cured product was measured by a laser flash method.

[Package crack resistance]
(1) IR reflow resistance A 6 mm x 6 mm silicon chip is mounted on a copper frame using the obtained resin paste, and heat curing (HP curing) at 200 ° C for 60 seconds or using an oven on a hot plate. And heat curing (OV curing) at 200 ° C. for 60 minutes. A package molded under the following conditions using an epoxy sealing material (trade name KE-G3000D) manufactured by Kyocera Chemical Co., Ltd. was subjected to moisture absorption treatment at 85 ° C. and relative humidity 85% for 168 hours, followed by IR reflow treatment (260 And the number of internal cracks in the package was observed with an ultrasonic microscope. The number of samples in which cracks occurred for five samples is shown.

Package: 80pQFP (14mm x 20mm x 2mm thickness)
Chip: Silicon chip and gold-plated chip on the back surface Lead frame: PPF and copper Molding of sealing material: 175 ° C., 2 minutes Post mold cure: 175 ° C., 8 hours

(2) TCT resistance Furthermore, as one of the long-term reliability evaluations of semiconductor devices, after the moisture absorption reflow, a temperature cycle test was conducted under the following conditions, and after the temperature cycle, the number of cracks inside the package was confirmed. . Here, as a temperature cycle test condition, [low temperature state: held at −65 ° C. for 30 minutes, high temperature state: held at 150 ° C. for 30 minutes] is one cycle, and evaluation was performed under the condition of repeating 1000 cycles.

All the above evaluation results are shown in Table 1.

  From the above, the thermosetting epoxy resin composition for semiconductor bonding of the present invention can exhibit excellent heat conduction characteristics more than solder even by low-temperature sintering, and can join metal substrates to each other without pressure, Semiconductor elements that have not been subjected to metal plating can also be bonded. It was also found that when a solvent functioning as a reducing agent such as alcohol was used as the solvent, a good bonding state could be formed with copper as a base metal, and the bonding strength and specific resistance could be improved.

Claims (6)

(A) a (meth) acrylic acid ester compound or a (meth) acrylamide compound having a hydroxyl group;
(B) a radical initiator;
(C) Silver fine particles having an average particle diameter of 10 to 100 nm, which is provided with a coating layer of an organic compound on the surface or dispersed in an organic compound;
(D) silver powder having an average particle diameter of 0.5 to 30 μm, and (E) a solvent;
A thermosetting resin composition for bonding semiconductors, characterized in that is an essential component. The thermosetting resin composition for semiconductor bonding according to claim 1, wherein the component (A) is a compound selected from the following general formulas (I) to (IV).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic hydrocarbon group having 1 to 100 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure.)

(In the formula, R ¹ and R ² are the same as described above.)

(Wherein, ^{R 1} represents the same as above, n is an integer of 1 to 50.)

(Wherein R ¹ and n each represent the same as above)   The thermosetting resin composition for semiconductor adhesion according to claim 1, wherein the component (E) is an alcohol (hydroxy compound) that functions as a reducing agent.   The thermosetting resin composition for semiconductor bonding according to any one of claims 1 to 3, wherein a mass ratio of the component (C) and the component (D) is 10:90 to 90:10. object.   The said (A) component contains 1-20 mass parts with respect to 100 mass parts of total amounts of the said (C) component and the said (D) component, The any one of Claims 1-4 characterized by the above-mentioned. A thermosetting resin composition for semiconductor bonding.   A semiconductor device comprising a semiconductor element bonded onto a semiconductor element support member using the thermosetting resin composition for semiconductor bonding according to any one of claims 1 to 5.