JP2015183093A - Composition suitable to interlaminar filler for lamination type semiconductor device, lamination type semiconductor device, and method for producing lamination type semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer filler composition for a lamination type semiconductor device capable of forming an interlayer filler layer having excellent thermal conductivity, even suitable to the lamination process of a semiconductor, also capable of secure joining between the semiconductor substrates and maintaining the stable joining in accordance with various environmental changes as well, a lamination type semiconductor device, and a production method therefor.SOLUTION: Provided is an interlayer filler composition for a lamination type semiconductor device containing: a resin whose melt viscosity at 120°C is 0.001 to 1 Pa s, a silica filler in which the volume average particle diameter is 0.1 to 10 μm; and an inorganic filler in which the volume average particle diameter is 0.1 to 10 μm, and also having the volume average particle diameter different from the average particle diameter of the silica filler.

Description

  The present invention relates to a composition suitable for an interlayer filler of a stacked semiconductor device, and a method for manufacturing a stacked semiconductor device using the composition and passing through a specific process.

In recent years, in order to improve the performance of semiconductor devices such as higher speed and higher capacity, in addition to miniaturization of transistors and wiring, a stacked semiconductor device in which two or more substrates used in a semiconductor device are stacked and stacked is used. Research and development is ongoing.
More specifically, a structure in which semiconductor substrates are connected to each other by an electrical signal terminal such as a solder bump between the chips and at the same time bonded by an interlayer filling layer formed by filling an interlayer filler. A stacked semiconductor device is known (for example, see Patent Document 1).

  Various problems have been pointed out for the practical application of such a stacked semiconductor device, and one of them is a problem of heat dissipation from a device such as a transistor or a wiring. This problem is generally caused by the fact that the thermal conductivity of the interlayer filler composition used when stacking semiconductor substrates is very low compared to metals and ceramics. There is concern about the performance degradation of semiconductor devices due to heat storage.

  One technique for solving this problem is to increase the thermal conductivity of the interlayer filler composition. Specifically, a highly thermally conductive epoxy resin is used as the thermosetting resin constituting the adhesive component of the interlayer filler composition, or such a highly thermally conductive resin and a highly thermally conductive inorganic filler are combined. By doing so, the interlayer filler composition is made to have high thermal conductivity. For example, an interlayer filler composition containing a spherical boron nitride aggregate as a filler is known (see, for example, Patent Document 2).

  The interlayer filler composition in which such a high heat conductive resin and a high heat conductive inorganic filler are combined contains a high heat conductive inorganic filler that is a solid, and therefore, temperature conditions when manufacturing a stacked semiconductor device. But usually the fluidity is low. Therefore, such an interlayer filler composition is difficult to fill between the semiconductor device chips after the semiconductor device chips are preliminarily connected with electrical signal terminals such as bumps. Therefore, a process is known in which a layer made of an interlayer filler composition is formed in advance and a semiconductor substrate is bonded.

  Specifically, a layer made of an interlayer filler composition (interlayer filler layer forming composition) is formed on a wafer on which semiconductor circuit elements are formed, heated to be B-staged, and then a chip is formed by dicing. A process has been proposed in which a plurality of chips are stacked, temporary bonding by heating and pressing is repeated, and finally final bonding (solder bonding) is performed under heating and pressing conditions (for example, see Non-Patent Document 1). ).

International Publication No. 2008/088771 Pamphlet Japanese translation of PCT publication No. 2008-510878

Proceedings of the Japan Institute of Electronics Packaging, 61, 23, 2009)

As described in the background art above, in the stacked semiconductor device, even the interlayer filler composition described in Patent Document 2 exhibits a thermal conductivity that can sufficiently dissipate heat generated due to the higher density of the integrated circuit. Was not reached. In addition, in a laminated semiconductor device, various required characteristics such as an appropriate linear expansion coefficient and a glass transition temperature are provided in order to relieve stress due to exothermic expansion during use of the laminated body in addition to improvement in thermal conductivity. The challenge that must be met was found.
In a process for manufacturing a stacked semiconductor device having an interlayer filler composition between layers of semiconductor substrates (hereinafter sometimes abbreviated as a stacking process), the interlayer filler composition is heated and pressurized. In addition to the improvement in viscosity and thermal conductivity that are suitable for bonding under conditions, there is a problem that the characteristics required in each process such as linear expansion coefficient must be satisfied to relieve the stress of the laminate. It was.

Furthermore, according to the present invention, not only the suitability for the lamination process but also the thinning of the layers between the semiconductor substrates, the bondability of the electrical signal terminals between the semiconductor substrates, and their stability (reliability) have been known. No issues were revealed. In particular, since the semiconductor substrate and the organic substrate in the stacked semiconductor device body have a low linear expansion coefficient, if the interlayer expansion material has a high linear expansion coefficient, the difference between the expansion coefficient due to the temperature change of the substrate, Issues such as causing delamination at the interface of the interlayer filling material were revealed.
The present invention is not only excellent in thermal conductivity, but also has a low coefficient of linear expansion when used as an interlayer filling material, so that it is suitable for a substrate lamination process, and further ensures reliable electrical connection between semiconductor substrates. A composition suitable for an interlayer filling material for a stacked semiconductor device capable of forming an interlayer filling layer, which can be bonded to each other and can be maintained stably by various environmental changes; It is an object of the present invention to provide a method for manufacturing a stacked semiconductor device using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific composition can solve the above problems, and have completed the present invention. That is, the gist of the present invention is as follows.
[1] A resin (A) having a melt viscosity of 0.001 to 1 Pa · s at 120 ° C., a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and an inorganic filler (E) that is not silica A composition containing
[2] The composition according to [1], wherein the inorganic filler (E) has a volume average particle size of 0.1 μm or more and 10 μm or less.
[3] The composition according to [1] or [2], wherein a difference in volume average particle size between the silica filler (B) and the inorganic filler (E) is 1 μm or more and 5 μm or less.
[4] The composition according to any one of [1] to [3], wherein the silica filler (B) has a specific surface area of 0.1 m ² / g or more and 100 m ² / g or less.
[5] The composition according to any one of [1] to [4], wherein the specific surface area of the inorganic filler (E) is 0.1 m ² / g or more and 20 m ² / g or less.
[6] The content of the silica filler (B) is 40 to 400 parts by weight with respect to 100 parts by weight of the resin (A), according to any one of [1] to [5]. Composition.
[7] The composition according to any one of [1] to [6], wherein the resin (A) is a thermosetting resin.
[8] The composition according to any one of [1] to [7], wherein the resin (A) is an epoxy compound (a).
[9] The composition according to [8], wherein the epoxy compound (a) includes an epoxy compound (a-1) having an epoxy equivalent of 150 g / equivalent to 650 g / equivalent.
[10] The composition according to [8] or [9], further comprising a curing agent (C).
[11] The composition according to any one of [1] to [10], further comprising a flux (D).
[12] A resin (A) having a melt viscosity of 0.001 to 1 Pa · s at 120 ° C., a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and an inorganic filler (E) that is not silica A method for producing a composition comprising: mixing at least two of all constituent components under a temperature condition of 40 ° C to 160 ° C.
[13] The method for producing a composition according to [12], wherein at least two of all components are mixed under a pressure condition of 100 Torr or less.
[14] A layer made of the composition according to any one of [1] to [11] is formed on the surface of the semiconductor substrate by a pre-apply method, and the semiconductor substrate and another substrate are stacked and heated and pressed. After joining, the manufacturing method of a laminated semiconductor device including the process processed at 50 to 200 degreeC.
[15] The method for manufacturing a stacked semiconductor device according to [14], wherein the other substrate is a semiconductor substrate.
[16] The method for manufacturing a stacked semiconductor device according to [14] or [15], wherein at least one of the semiconductor substrates is a semiconductor substrate having a semiconductor circuit element.
[17] A stacked semiconductor device in which at least two semiconductor substrates each having a semiconductor circuit element are stacked, wherein at least one of the semiconductor substrates is provided with any one of [1] to [11] A laminated semiconductor device having a layer formed by curing an interlayer filler composition.

  According to the present invention, a composition having excellent compatibility with a manufacturing process of a stacked semiconductor device and a performance balance such as thermal conductivity, heat resistance, mechanical strength, etc., and a semiconductor having a layer made of the composition Provided is a composition suitable as an interlayer filler for a stacked semiconductor device, in which reliable electrical bonding between a semiconductor substrate and another substrate is possible in the device, and the electrical bonding can be stabilized. be able to. Also provided is a method for manufacturing a stacked semiconductor device, comprising a step of forming a layer made of a composition for an interlayer filler provided by the present invention between a substrate and treating it under specific conditions. be able to.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
The present invention includes a resin (A) having a melt viscosity at 120 ° C. of 0.001 to 1 Pa · s, a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and a volume average particle size of 0.1 μm. The present invention relates to a composition suitable for an interlayer filler for a laminated semiconductor device containing an inorganic filler (E) of 10 μm or less (hereinafter sometimes simply referred to as “composition”).

Here, the stacked semiconductor device of the present invention is a stacked body having a semiconductor substrate on which a wiring circuit, a through electrode (TSV), a semiconductor element circuit, and the like are formed. The semiconductor substrate may be provided with a through electrode (TSV), and the substrates are connected via bumps. In the stacked semiconductor device of the present invention, a composition suitable for the interlayer filler according to the present invention is used between the layers of the stacked body.
As a process for forming such a stacked semiconductor device, for example, after forming a coating thin film of an interlayer filler composition on a wafer, a B-stage is performed as necessary, tackiness is reduced, and then dicing is performed. A process is proposed in which a semiconductor chip is cut out, a laminated body is obtained by temporary bonding using the semiconductor chip, and finally main bonding (solder bonding) is performed under heating and pressing conditions.

When such a process is employed, the composition used for the interlayer filler preferably has low fluidity at room temperature and a low melt viscosity at the time of solder joining. On the other hand, the interlayer filler composition is required to have a low coefficient of linear expansion in addition to suitability for the above manufacturing process and high thermal conductivity. In order to achieve a low coefficient of linear expansion, it is effective to combine a boron nitride filler with a high thermal conductivity and an inorganic filler. The resin (A) having a melt viscosity of 0.001 to 1 Pa · s at 120 ° C., a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and an inorganic filler that is not silica (E And a composition suitable for an interlayer filler for a stacked semiconductor device, which is suitable for the required performance, and further contains a curing agent (C), etc. It can be a thing.

<Resin (A)>
As the resin (A) used in the present invention, one having a melt viscosity at 120 ° C. of 0.001 to 1 Pa · s is used.
-Viscosity The viscosity at 120 ° C of the resin (A) according to the present invention can be measured using a commercially available melt viscometer. More specifically, for example, it is a parallel plate dynamic viscosity measured using a viscoelasticity measuring apparatus Physica MCR301 manufactured by Anton Paar Japan Co., Ltd. The measuring method is as follows.

・ Viscosity measurement method If the resin is liquid at room temperature, if it is solid at room temperature, heat it and cool it to room temperature to obtain an amorphous solid. Place between plates (φ25mm) and measure parallel plate dynamic viscosity. The measurement condition is that 20% sinusoidal distortion is applied to the sample, the angular frequency of the distortion is 10 rad / sec, and the viscosity in the process of raising the temperature at a rate of 3 ° C. per minute is measured from 40 ° C. to 200 ° C. .

・ Control of viscosity To adjust the viscosity of the resin (A) at 120 ° C. to 0.001 to 1 Pa · s, a conventionally known method of adjusting the viscosity of the high molecular weight material is used. For example, the molecular weight of the resin is adjusted. Or introducing a highly flexible chain such as an aliphatic hydrocarbon group into the resin skeleton to lower the viscosity, or introducing a less flexible chain such as a ring structure or a structure having a bridgehead. This can be achieved by increasing the viscosity, mixing a high-viscosity resin and a low-viscosity resin, or decreasing the viscosity using a resin (compound) having a clear melting point. A resin having a melting point is a substance that exists as a solid that is stable in a crystalline state at room temperature, but quickly dissolves as soon as the melting point is reached, and becomes a very low-viscosity liquid. This means that the change in state can be confirmed.

-Chemical structure of resin (A) There is no particular limitation on the type of resin (A), and epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, polyester resin, allyl resin, alkyd resin, urethane resin, silicone resin, Any resin such as an acrylic resin or a polyimide resin may be used, but one having a certain mechanical strength suitable for use in a semiconductor device is preferable. More preferably, those having a mesogen as a structural unit can be used so that heat generated when the semiconductor device is used can be efficiently transferred. As used herein, mesogen refers to a structural unit that is a rigid structural unit and can be a polymer liquid crystal. Examples of such a mesogen include a structural unit having a plurality of benzene rings or a condensed structural unit.

Examples of such mesogens include biphenyl, cyanobiphenyl, terphenyl, cyanoterphenyl, phenylbenzoate, azobenzene, azomethine, azoxybenzene, stilbene, phenylcyclohexyl, biphenylcyclohexyl, phenoxyphenyl, benzylideneaniline, benzylbenzoate, phenyl Examples include pyrimidine, phenyldioxane, benzoylaniline, tolan and the like and substituted products thereof. Examples of this substituent include one or a plurality of alkyl groups having 1 to 18 carbon atoms that can be substituted on the benzene ring, and a plurality of benzene rings or hydrogenated partially condensed rings.

  The mesogen may have at least one in one molecule of the repeating structural unit in the resin, and may have two or more mesogens. Moreover, it is preferable that the connection part of a some mesogen and the terminal part of a mesogen are comprised by the flexible structure part called a bending chain (spacer). Examples of the flexible structure include an aliphatic hydrocarbon group, an aliphatic ether group, an aliphatic ester group, and a siloxane bond.

  The resin (A) of the present invention preferably has a property of becoming a liquid crystal state in which mesogens are regularly arranged in a predetermined temperature range. This liquid crystallinity can be confirmed by a polarization inspection method using an orthogonal polarizer, and a liquid crystalline reaction curable resin in a liquid crystal state exhibits strong birefringence. Examples of the liquid crystal state include nematic, smectic, cholesteric, and discotic.

  Examples of the resin having a certain mechanical strength suitable for use in a semiconductor device include an epoxy resin, a phenol resin, a urea resin, a melamine resin, a urethane resin, a silicon resin, and a polyimide resin. Among these resins, thermosetting resins excellent in heat resistance and various electric characteristics are preferable, and those that are not thermally decomposed by heating during the main bonding (solder bonding) are preferable. More specifically, such a resin is preferably a resin having a thermal decomposition starting temperature of 180 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 220 ° C. or higher. Examples of such a resin include an epoxy resin and a polyimide resin. Particularly preferably, an epoxy resin is used. In the resin (A), these resins may be used alone or in combination of two or more.

・ Epoxy compound (a)
The epoxy compound (a) particularly preferred as the resin (A) according to the present invention preferably contains an epoxy compound (a-1) having a viscosity at 120 ° C. of 1 Pa · s or less. The epoxy compound (a) preferably has two or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin. , Cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, polyfunctional phenol type epoxy resin Bisphenol A type or bisphenol F type solid epoxy resin, phenoxy resin, or the like can be used. These can be used alone or as a mixture of two or more.

  From the viewpoint of controlling the melt viscosity, the epoxy equivalent is preferably 150 g / equivalent to 650 g / equivalent, more preferably 175 g / equivalent to 600 g / equivalent. When the epoxy equivalent is less than 150 g / equivalent, the heat resistance tends to be inferior. When the epoxy equivalent is higher than 650 g / equivalent, the melting point of the epoxy compound is increased and the melt viscosity of the composition according to the present invention is increased. There is a problem in chip-to-chip bonding, the stacked semiconductor device may not function effectively, and physical properties required in each step of the 3D stacking process cannot be satisfied, and it is difficult to manufacture the stacked semiconductor device. There is a risk of becoming.

The proportion of the epoxy compound (a-1) in the resin (A) contained in the composition of the present invention is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, based on the total amount of the resin (A).
99% by weight.
More specifically, commercially available bisphenol A type epoxy resin (YL6810; viscosity at 120 ° C of 0.008 Pa · s or less), bisphenol F type epoxy resin (1750; viscosity at 120 ° C of 0) available from Mitsubishi Chemical Corporation. 0.01 Pa · s or less), biphenyl type epoxy resin (YX4000 (H); viscosity at 120 ° C. of 0.03 Pa · s or less, YL6121H; viscosity at 120 ° C. of 0.02 Pa · s or less), anthracene epoxy resin (YX8800), Examples include bisphenol type epoxy resins (YSLV-80XY, YSLV-120TE) manufactured by Nippon Steel Chemical Co., Ltd., hydroquinone type epoxy resins (YDC-1312), and naphthalene type epoxy resins (HP4032D) manufactured by DIC Corporation.

These epoxy compounds may be used individually by 1 type, and may mix and use 2 or more types.
Further, the composition of the present invention may be abbreviated as an epoxy compound (a-2) other than the epoxy compound (a-1) (hereinafter referred to as an epoxy compound (a-2)) as long as the purpose is not impaired. Can be included).

  Examples of other epoxy compounds (a-2) are preferably those having two or more epoxy groups in the molecule, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and naphthalene type epoxy resins. , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, A polyfunctional phenol type epoxy resin, a bisphenol A type or bisphenol F type solid epoxy resin, a phenoxy resin, or the like can be used. These can be used alone or as a mixture of two or more.

  From the viewpoint of controlling the melt viscosity, the epoxy equivalent is preferably more than 650 g / equivalent and 30000 g / equivalent or less, more preferably 800 g / equivalent to 25000 g / equivalent. When the epoxy equivalent is 650 g / equivalent or less, even if it is used in combination, sufficient physical properties cannot be obtained as a composition used for the interlayer filler, and if it is greater than 30000 g / equivalent, the melting point of the epoxy compound becomes high, Workability tends to decrease.

  When the composition of this invention contains another epoxy compound (a-2), in the composition of this invention, in all the epoxy compounds containing an epoxy compound (a-1) and another epoxy compound (a-2) The ratio of the epoxy compound (1a) is 75 to 99% by weight, preferably 80 to 95% by weight, with the total being 100% by weight. In addition, "all the epoxy compounds containing an epoxy compound (a-1) and another epoxy compound (a-2)" means the sum total of an epoxy compound (a-1) and another epoxy compound (a-2). To do.

<Silica filler (B)>
The composition of the present invention contains a silica filler (B) having a volume average particle size of 0.1 μm or more and 10 μm or less. In the present invention, any silica filler (B) can be used as long as the silica filler (B) has at least a volume average particle diameter of 0.1 μm or more and 10 μm or less. More specifically, for example, crystalline silica obtained by pulverizing natural silica, amorphous silica such as quartz glass, fused silica, and synthetic silica can be used. These can be used alone or as a mixture of two or more.

In the composition of the present invention, the silica filler (B) is mainly intended to improve the thermal conductivity, but when it is contained between the layers of the stacked semiconductor device in combination with the inorganic filler (E) described later, It contributes to achieving high thermal conductivity and low coefficient of linear expansion at the same time.
The silica filler (B) according to the present invention preferably has a volume average particle size of 10 μm or less. Further, the silica filler (B) according to the present invention preferably has a volume average particle size of 7 μm or less, more preferably 5 μm or less, and particularly preferably 4 μm or less. On the other hand, the volume average particle diameter is preferably 0.1 μm or more from the viewpoint of obtaining good thermal conductivity and good fluidity.

  The volume average particle size of the silica filler (B) in the present invention is, for example, dispersed in an appropriate solvent, measured by a laser diffraction / scattering type particle size distribution measuring device, etc., and the volume distribution from the obtained particle size distribution. The average particle size can be determined. Specifically, for example, it can be measured with a laser diffraction / scattering particle size distribution measuring device “LA-920” manufactured by Horiba.

Usually, the specific surface area of the silica filler (B) is 0.1 m ² / g or more, preferably 0.1 m ² / g or more 100 m ² / g or less, more preferably 0.5 m ² / g or more ^{50 m} 2 / g or less, more preferably 1 m ² / g or more and 10 m ² / g or less.
In addition, the specific surface area of a silica filler (B) can be measured by the BET 1 point method (adsorption gas: nitrogen). More specifically, the specific surface area of the silica filler (B) is a value measured by the method described in the Examples section described later.

  The silica filler (B) according to the present invention is preferably spherical. In the present invention, “spherical” refers to those having an aspect ratio (ratio of major axis to minor axis) of 1 or more and 2 or less. The aspect ratio is preferably 1 or more and 1.5 or less. The aspect ratio of the particles is determined by arbitrarily selecting 200 or more particles from an image taken with a scanning electron microscope (SEM), calculating the ratio of the major axis to the minor axis, and calculating the average value. .

In addition, immediately after manufacture, the silica filler (B) may further agglomerate the obtained particles and may not satisfy the above particle diameter range. Therefore, the silica filler (B) is preferably used after being pulverized so as to satisfy the above particle diameter range. The method of pulverizing the particles is not particularly limited, and a conventionally known pulverization method such as a method of stirring and mixing with a pulverizing medium such as zirconia beads or a jet injection can be applied. Moreover, the volume average particle diameter can also be adjusted by removing or adding particles having different particle diameters with a sieve or the like.
In the case where the composition is used by including the silica filler (B) according to the present invention, the silica filler (B) may be used alone or in combination of two or more having different physical properties. Also good.

Two or more types of silica fillers (B) having different average particle diameters may be used. That is, silica filler (B) having a relatively small average particle size, for example, 0.1 to 2 μm, preferably 0.2 to 1.5 μm, and a relatively large average particle size, for example, 1 to 5 μm, preferably 1 By using together with a silica filler (B) of ˜3 μm, the same average is obtained by connecting the heat conduction paths between silica fillers (B) having a large average particle diameter with silica fillers (B) having a small average particle diameter. Compared with the case of using only particles having a particle size, high filling is possible, and higher thermal conductivity can be obtained.
In this case, the silica filler (B) having a small average particle diameter and the silica filler (B) having a large average particle diameter are used in a weight ratio of 10: 1 to 1:10 in order to form a heat conduction path. Is preferable.
Moreover, when using a silica filler (B), in order to improve the dispersibility in resin (A) or a coating liquid, you may perform a surface treatment suitably.

(Maximum particle size based on volume)
The silica filler (B) according to the present invention preferably has a volume-based maximum particle size in the range of 0.1 to 20 μm, particularly 0.3 to 15 μm, especially 0.5 to 10 μm. When the maximum particle diameter of the silica filler (B) is not more than the above upper limit, when used as the boron nitride filler (B) of the composition, an interlayer filling layer having no surface roughness can be formed. Further, it is possible to form a thin interlayer filling layer, which can be suitably used for thin film coating, and the thermal conductivity in the thickness direction can be increased. In the silica filler (B) whose maximum particle size is smaller than the above lower limit, the thermal conductivity improving effect as the thermal conductive filler is reduced.
Although no particular limitation on the average particle diameter D ₅₀ based on volume of the silica filler according to the present invention (B), for the same reason the value of the maximum particle size of the volume-based, is 0.1~20μm It is preferably 0.3 to 10 μm, more preferably 0.5 to 5 μm.

  In general, in a stacked semiconductor device, the distance between chips is reduced to about 10 to 50 μm between chips in order to further improve performance such as higher speed and higher capacity. In the interlayer filler layer, the maximum particle size of the filler to be blended is preferably set to 1/2 to 1/3 or less of the thickness of the interlayer filler layer.

When the maximum particle diameter of the silica filler (B) exceeds 10 μm, the silica filler (B) protrudes on the surface of the interlayer filling layer after curing, and the surface shape of the interlayer filling layer tends to deteriorate.
On the other hand, if the particle size of the silica filler (B) is too small, the number of necessary heat conduction paths increases, and the probability of connection from the top to the bottom in the thickness direction between the chips decreases, and a resin with high thermal conductivity ( Even in combination with A), the thermal conductivity in the thickness direction of the interlayer filling layer becomes insufficient.
Moreover, when the particle size of a silica filler (B) is too small, a silica filler (B) will aggregate easily and the dispersibility in a composition or a coating liquid will worsen. The average particle diameter D ₅₀ of the silica filler (B), by the above-described range, excessive agglomeration of filler grains can be suppressed, it is possible to obtain an interlayer filling layer having sufficient thermal conductivity in the thickness direction.

<Inorganic filler (E)>
The inorganic filler (E) used in the present invention is a filler that is not silica (silicon oxide).
In the composition of the present invention, the inorganic filler (E) is added for the purpose of improving thermal conductivity and controlling the linear expansion coefficient. By having a volume average particle size different from the volume average particle size of the silica filler (B), it becomes possible to mutually fill the voids between the particles in the composition with the silica filler (B), and heat It has a remarkable effect on the improvement of conductivity and the control of the linear expansion coefficient, but particularly contributes to the control of the linear expansion coefficient.

  Examples of the inorganic filler (E) include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of carbon include carbon black, carbon fiber, graphite, fullerene and diamond. Examples of the metal carbide include silicon carbide, titanium carbide, tungsten carbide and the like. Examples of metal oxides include magnesium oxide, aluminum oxide, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, sialon (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Moreover, there is no restriction | limiting about those shapes, A particulate form, a whisker form, a fiber form, plate shape, or those aggregates may be sufficient. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride.

In the highly heat conductive resin composition, metal oxide and metal nitride are preferable among the inorganic fillers (E) because there are many uses that require insulation.
More specifically, examples of the inorganic filler (E) include alumina (Al ₂ O ₃ ), boron nitride (BN), aluminum nitride (AlN), magnesium oxide (MgO), and among them, Al ₂ O ₃ is preferable. . These inorganic fillers (E) may be used alone or in a combination of two or more in any combination and ratio.

  The inorganic filler (E) of the present invention preferably has a volume average particle size of 10 μm or less. The inorganic filler (E) of the present invention preferably has a volume average particle size of 7 μm or less, more preferably 5 μm or less, and particularly preferably 4 μm or less. On the other hand, from the viewpoint of obtaining good thermal conductivity and good fluidity, the volume average particle size is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.5 μm or more.

  In the present invention, the volume average particle diameter of the silica filler (B) is different from the volume average particle diameter of the inorganic filler (E). In order to achieve both improved thermal conductivity and control of the linear expansion coefficient, The difference between the volume average particle diameter of the silica filler (B) and the volume average particle diameter of the inorganic filler (E) is preferably 1 μm or more and 5 μm or less, more preferably 2 μm or more and 4 μm or less.

  When the composition of the present invention contains an inorganic filler (E) having high thermal conductivity in addition to the silica filler (B) having high fluidity, an interlayer filling layer is formed using this composition. At the same time as improving the heat conduction between semiconductor substrates, the linear expansion coefficient of the interlayer filling layer is reduced, and the possibility of damage to the stack due to mismatch of the linear expansion coefficient with the semiconductor device substrate is reduced, making the semiconductor device stable. It becomes possible to operate.

In recent years, the distance between chips has been reduced to about 10 to 50 μm in order to improve performance such as higher speed and higher capacity. The maximum particle size of the filler to be blended is preferably 1/3 or less of the thickness of the interlayer filling layer.
If the maximum particle size of the inorganic filler (E) exceeds 10 μm, the inorganic filler (E) protrudes from the surface of the interlayer filling layer after curing, and the surface shape of the interlayer filling layer tends to deteriorate.

  On the other hand, if the particle size of the inorganic filler (E) is too small, the inorganic filler (E) tends to aggregate and the dispersibility in the composition or the coating solution is deteriorated. On the other hand, if the particle size of the inorganic filler (E) is too small, the specific surface area increases and the viscosity of the composition increases, making it difficult to apply to the 3D lamination process. In the present invention, by setting the volume average particle diameter of the inorganic filler (E) within the above range, excessive aggregation of the fillers can be suppressed and an interlayer filler layer having good thermal conductivity can be obtained.

Note that the inorganic filler may not meet the above particle size range because the powder aggregates immediately after synthesis. Therefore, it is preferable to pulverize and use the inorganic filler so as to satisfy the above particle size range.
The method for pulverizing the inorganic filler is not particularly limited, and a conventionally known pulverization method such as pulverization using a roll mill or a planetary mixer, stirring and mixing with a pulverizing medium such as zirconia beads, or jet injection can be applied.

In the present invention, the above inorganic fillers may be used alone or in combination of two or more inorganic fillers having different physical properties.
For example, two or more inorganic fillers having different volume average particle diameters may be used. That is, an inorganic filler having a relatively small volume average particle diameter, for example, 0.1 to 2 μm, preferably 0.2 to 1.5 μm, and a relatively large volume average particle diameter, for example, 1 to 5 μm, preferably 1 to By using together with a 3 μm inorganic filler, by connecting the heat conduction paths of inorganic fillers having a large volume average particle diameter with inorganic fillers having a small volume average particle diameter, only those having the same volume average particle diameter were used. Higher filling is possible than in the case, and higher thermal conductivity can be obtained.

In this case, the inorganic filler having a small volume average particle diameter and the inorganic filler having a large volume average particle diameter are preferably used in a weight ratio of 10: 1 to 1:10 in terms of forming a heat conduction path.
In addition, the inorganic filler (E) may be appropriately surface-treated with, for example, a silane coupling agent in order to enhance the dispersibility in the resin (A) or the coating solution. As the silane coupling agent, those having at least one group selected from a vinyl group, an epoxy group, an amino group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group as a functional group are preferable. It is more preferable to have

  The content of the inorganic filler (E) in the composition of the present invention is preferably 10 to 400 parts by weight, more preferably 20 to 300 parts by weight, per 100 parts by weight of the resin (A). When the content of the inorganic filler (E) is less than 10 parts by weight per 100 parts by weight of the total epoxy compound, the effect of adding the inorganic filler (E) is reduced, and the desired effect of reducing the linear expansion coefficient cannot be obtained. When the amount exceeds 400 parts by weight, the presence of the inorganic filler (E) may inhibit the bonding property.

<Physical properties of silica filler (B) and inorganic filler (E)>
-Volume average particle diameter The silica filler (B) and the inorganic filler (E), when the particle diameter is too large, inhibits electrical bonding between semiconductor chips on which the semiconductor device layers of the stacked semiconductor device are formed, There may be a problem that electrical bonding between semiconductor chips once bonded is cut due to a temperature change or the like. Further, if it is too small, it tends to agglomerate, dispersibility in the composition is deteriorated, and viscosity increase and poor bonding occur. Therefore, it is necessary to control the volume average particle diameter defined in the present invention already described. is there.

  The volume average particle diameter of the silica filler (B) and the inorganic filler (E) can be measured by a generally known particle size distribution measuring device, and can be measured by, for example, the following method. The composition is dispersed in cyclohexanone at a desired concentration and measured with a particle size distribution analyzer “SALD-2200” manufactured by Shimadzu Corporation to obtain a volume particle size distribution. From the obtained particle size distribution, the volume average particle size of the pulverized inorganic filler can be obtained.

Specific surface area The specific surface areas of the silica filler (B) and the inorganic filler (E) can be measured by a conventionally known specific surface area measurement method such as a gas adsorption method, and can be measured by, for example, the following method. After pretreatment of nitrogen gas flow for 15 minutes at 250 ° C. for inorganic filler (E), specific surface area is measured by BET 1-point method (adsorbed gas: nitrogen) using Macsorb HM MODEL-1201 manufactured by Mountec Co., Ltd. can do.

-Thermal conductivity The thermal conductivity of the inorganic filler (E) can be measured by forming a thin plate by sintering or the like by a steady method or an unsteady method. In the unsteady method, the thermal conductivity λ is proportional to the thermal diffusivity (α), the specific heat capacity (Cp), and the density (ρ). Therefore, for example, α, Cp, and ρ are obtained according to the method specified in JIS R1611. Thereafter, the thermal conductivity λ can be measured by these products.

<Curing agent (C)>
The composition of this invention may contain the hardening | curing agent (C) as needed. The hardening | curing agent (C) used by this invention shows the substance which contributes to the crosslinking reaction between the epoxy groups of an epoxy compound.
There is no restriction | limiting in particular as a hardening | curing agent (C), Generally, what is generally known as a hardening | curing agent of an epoxy compound can be used. For example, phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and the like Derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like. Moreover, these hardening | curing agents (C) may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cle Lour novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, 1,2,4-benzenetriol, 2, 3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy Futaren, 2,8-dihydroxynaphthalene, allyl compound or polyallyl compound of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, polyallyl of pyrogallol and the like.

Specific examples of the amine curing agent include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, Examples include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) Ethylamine, diaminodiethyl Examples thereof include dimethyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Examples of the anhydride include 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

Examples of the amide type curing agent include dicyandiamide and polyamide resin.
Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .
Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl -(1 ')]-ethyl-s-triazine, 2,4-diamino 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- Examples include 4-methyl-5-hydroxymethylimidazole, adducts of epoxy resin and the above imidazoles, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Is done.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

Moreover, the aromatic amine type hardening | curing agent shown by following formula (1) is mention | raise | lifted.
H ₂ N—Ar—COO— [X—O] —CO—Ar—NH ₂ (1)
Here, Ar represents a phenylene group.

In the formula (1), — [X—O] — represents at least one structure selected from — (CH ₂ ) _n —O—, — (CH ₂ CH ₂ O) _n —, and a branched structure thereof. means. This formula (1
N is preferably an integer of 1 to 20, preferably an integer of 2 to 16, more preferably 4 to 12, and most preferably 8 to 12. When n is too large, the elastic modulus and glass transition temperature of the cured product are lowered. On the other hand, when n = 0, the mobility of the mesogen in the epoxy compound is lowered due to the rigidity of the aromatic diamine. Are not preferable because the formation of a highly ordered domain phase is hindered and the thermal conductivity does not increase.

In addition, when-[XO]-is an ethylene glycol unit, in one molecule,-[XO]-in formula (1) is-(CH ₂ ) _n -O- The branched structure is more preferable in terms of industrial availability. Examples of such ingredients are:
Bis (4-aminobenzoyloxy) methane,
Bis (4-aminobenzoyloxy) ethane,
1,3-bis (4-aminobenzoyloxy) propane,
1,4-bis (4-aminobenzoyloxy) butane,
1,5-bis (4-aminobenzoyloxy) pentane,
1,6-bis (4-aminobenzoyloxy) hexane,
1,7-bis (4-aminobenzoyloxy) heptane,
1,8-bis (4-aminobenzoyloxy) octane,
1,9-bis (4-aminobenzoyloxy) nonane,
1,10-bis (4-aminobenzoyloxy) decane,
1,11-bis (4-aminobenzoyloxy) undecane,
1,12-bis (4-aminobenzoyloxy) dodecane and the like.

Content of the hardening | curing agent (C) in the composition of this invention is all the epoxy compounds containing the epoxy compound (a-1) whose viscosity in 150 degreeC is 1 Pa.s or less, and another epoxy compound (a-2). The amount is 0.005 to 200 parts by weight, preferably 0.01 to 180 parts by weight per 100 parts by weight.
If the content of the curing agent (C) per 100 parts by weight of the total epoxy compound is less than 0.005 parts by weight, curing may be insufficient. If it exceeds 200 parts by weight, adhesiveness, thermal conductivity, etc. The desired physical properties may not be obtained.

<Flux (D)>
The composition of the present invention preferably further contains a flux (D). Specifically, the flux means that the metal electrical signal terminal such as a solder bump and the surface oxide film of the land are dissolved and removed at the time of solder joining of the metal terminal, and the wetting and spreading property on the land surface of the solder bump is further improved. It is a compound having a function of preventing reoxidation of the surface of the metal terminal of the solder bump.

Examples of the flux used in the present invention include aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, and stearic acid. Organic carboxylic acids such as benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic anhydride, aromatic carboxylic acids such as trimesic acid, benzenetetracarboxylic acid, and terpene carboxylic acids such as abietic acid and rosin Organic carboxylic acid esters, glutamic acid hydrochlorides, aniline hydrochlorides, hydrazine hydrochlorides, cetylpyridine bromides, phenylhydrazine hydrochlorides, tetrachlors, which are hemiacetal esters converted by reacting acids and organic carboxylic acids with alkyl vinyl ethers Naphthalene, methylhydrazine hydrochloride, Organic halogen compounds such as tilamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride and butylamine hydrochloride, amines such as urea and diethylenetriamine hydrazine, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and glycerin , Inorganic acids such as hydrochloric acid, hydrofluoric acid, phosphoric acid, borohydrofluoric acid, fluorides such as potassium fluoride, sodium fluoride, ammonium fluoride, copper fluoride, nickel fluoride, zinc fluoride, potassium chloride, sodium chloride , Chlorides such as cuprous chloride, nickel chloride, ammonium chloride, zinc chloride, stannous chloride, bromides such as potassium bromide, sodium bromide, ammonium bromide, tin bromide, zinc bromide, etc. . These compounds may be used as they are or may be microencapsulated using a coating agent made of an organic polymer or an inorganic compound. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

  The content of the flux (D) in the composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight per 100 parts by weight of the resin (A). It is as follows. If the content of the flux (D) is less than 0.1 parts by weight per 100 parts by weight of the total epoxy compound, there is a risk of poor solder connection due to a decrease in oxide film removability, and if it exceeds 10 parts by weight, the viscosity of the composition increases. There is a risk of poor connection.

  The content of the flux (D) is preferably 5 parts by weight or more and preferably 10 parts by weight or more with respect to a total of 100 parts by weight of the resin (A), the silica filler (B), and the inorganic filler (E). When the amount is less than 5 parts by weight, the resulting resin composition has a small thermal conductivity, which is not preferable. On the other hand, the upper limit of the content is preferably 150 parts by weight, and preferably 100 parts by weight. When the amount is more than 150 parts by weight, the viscosity of the composite material is increased, and the silica filler (B) and the inorganic filler (E) are hardly dispersed uniformly. The same applies to the content when hexagonal boron nitride is used as the inorganic filler (E).

<Dispersant (F)>
The composition of the present invention increases the dispersibility of the silica filler (B) and the inorganic filler (E), so that a dispersant, a surfactant, an emulsifier, a low elastic agent, a diluent, an antifoaming agent, an ion trapping agent, etc. It is preferable to contain. As the dispersant, in order to enhance the dispersibility of the silica filler (B), it is preferable to use a dispersant having an amine value (mg-KOH / g) of 10 or more and 300 or less. Moreover, when using the composition of this invention as a compound using a dispersing agent, since it is excellent in the improvement of the applicability | paintability of a compound, and the improvement effect of a coating-film property, what has a tertiary amino group as a functional group is preferable. An example of such a dispersant (F) is an acrylic dispersant and / or a urethane dispersant.
As the surfactant, any of conventionally known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.

  For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl Examples include sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, and the like.

Further, in these surfactants, fluorine surfactants in which a part or all of the C—H bonds are C—F bonds can also be preferably used.
The addition amount of the surfactant is preferably about 0.001 to 5% by weight, more preferably 0.01 to 1% by weight, based on the total solid content in the composition. If it is less than 0.001% by weight, the dispersion characteristics of the inorganic filler (E) may not be improved, and if it exceeds 5% by weight, phase separation with the resin (A) may be caused, which is not preferable.

<Method for producing composition according to the present invention>
A composition suitable as an interlayer filler for a stacked semiconductor device according to the present invention can be produced by mixing the constituent components at the mixing ratio described above. At that time, for the purpose of improving the uniformity of the composition, defoaming, etc., it is preferable to mix using a paint shaker, a bead mill, a planetary mixer, a stirrer-type disperser, a self-revolving stir mixer, a triple roll or the like. Further, the mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two components or three or more components of the composition are mixed in advance, and then the remaining components are mixed. You may mix and may mix all at once.

  When mixing the constituents of the composition of the present invention, it is preferable to heat the constituents to room temperature or higher so that the constituents can be mixed more uniformly. More preferably, mixing is performed under a temperature condition of 40 ° C. or higher and 130 ° C. or lower. When mixing at a temperature of 40 ° C. or lower, the viscosity of the resin (A) may be high, which may make it difficult to uniformly disperse the inorganic filler. When mixed at a temperature of 130 ° C. or higher, bubbles are formed in the composition. There is a risk of mixing.

Moreover, mixing of bubbles when mixing the constituent components of the composition of the present invention can be reduced by lowering the pressure during mixing. More specifically, the pressure in the mixing tank is preferably 100 Torr or less, more preferably 90 Torr or less, and particularly preferably 80 Torr or less.
Furthermore, an organic solvent or a liquid resin may be used in combination for uniform mixing.

  Examples of the organic solvent used in the composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, Examples thereof include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.

Among these, considering the solubility of the resin and the boiling point of the solvent, ketones such as methyl ethyl ketone and cyclohexanone, esters and ethers are preferable, and ketones such as methyl ethyl ketone and cyclohexanone are particularly preferable.
These organic solvents may be used alone or in a combination of two or more in any combination and ratio.

  In the composition of the present invention, the mixing ratio of the organic solvent to the other components is not particularly limited, but preferably the solid content concentration in the composition is 20% by weight to 70% by weight, particularly 30% by weight to 60% by weight. It is preferable to use the organic solvent in such a ratio that it is not more than%. By setting the organic solvent to such a content ratio, a good coating film can be formed by any coating method using the composition of the present invention.

If the mixing ratio of the organic solvent is less than the above lower limit, the viscosity of the composition may increase and a good interlayer may not be obtained, or if it exceeds the above upper limit, a desired interlayer film thickness may not be obtained. There is a possibility of coming. The solvent can be removed by drying under reduced pressure after mixing.
A composition suitable as an interlayer filler for a laminated semiconductor device according to the present invention can be molded by heating and molding. This molding method can be appropriately performed according to the state of the composition and the type of resin using a generally used method.

  For example, the composition having plasticity or fluidity can be molded by curing the composition in a desired shape, for example, in a state of being accommodated in a mold. In the production of such a molded body, injection molding, injection compression molding, extrusion molding, and compression molding can be used. Moreover, shaping | molding of a molded object, ie, hardening, can be performed on each hardening temperature conditions. Moreover, the said molded object can be obtained also by cutting out the hardened | cured material of an interlayer filler composition in a desired shape.

[Other additives]
The composition of the present invention may contain various additives within a range not impairing the effects of the present invention for the purpose of further improving the functionality.
Examples of such additives include fine particle components for controlling the orientation of silica filler (B) and inorganic filler (E), and reactive diluent components that lower the composition without impairing the properties of the epoxy compound. In order to improve film properties such as elastic modulus and fracture toughness, resin components having a flexible skeleton and a rubber elastic skeleton, rubber-like particles of about 0.01 to 1 μm, alkali metal ions and halogen ions An ion scavenger for capturing ionic components such as

  As the fine particle component for controlling the orientation of the silica filler (B) and the inorganic filler (E), those having a volume average particle size of 0.5 μm or more and 20 μm or less are preferably used, and more preferably 1 μm or more and 10 μm or less. is there. Examples of such fine particle components include resin fine particles, fine particles based on methacrylic acid esters such as methyl methacrylate and butyl methacrylate, resins obtained from acrylic acid esters, and the like, their monomers and methyl vinyl ether. Copolymer fine particles with other monomers such as vinyl acetate and divinylbenzene, and acrylic fine particles such as fine particles obtained by crosslinking these; styrene fine particles; low density polyethylene fine particles, high density polyethylene fine particles, ultrahigh molecular weight polyethylene fine particles, and Polyethylene fine particles such as ethylene / acrylic acid copolymer fine particles; nylon fine particles; PAN fine particles mainly composed of polyacrylonitrile; thermosetting and thermoplastic polyurethane fine particles; novolac resin fine particles, resole resin fine particles, etc. Nord resin fine particles; Silicone resin fine particles such as silicone resin fine particles and silicone resin coated fine particles; benzoguanamine / melamine fine particles such as benzoguanamine / formaldehyde condensate fine particles, benzoguanamine / melamine / formaldehyde condensate fine particles, melamine / formaldehyde condensate fine particles; Fluorine resin fine particles such as tetrafluoroethylene resin fine particles; Engineering plastic fine particles such as aramid fine particles, polyimide fine particles, and PEEK fine particles; Natural polymer fine particles such as silk.

  Further, as the inorganic fine particles, it is possible to use insulating fine particles that are chemically different from the silica filler (B) and the inorganic filler (E) of the present invention. Here, “chemically different” includes not only the case where the types of constituent elements are different but also the case where the ratios of constituent elements are different. Specifically, for example, inorganic oxides such as aluminum oxide (alumina), magnesium oxide, beryllium oxide, zinc oxide, calcium oxide, zirconium oxide; inorganic nitrides such as aluminum nitride, silicon nitride, boron nitride; silicon carbide, titanium carbide And fine particles such as inorganic carbides such as boron carbide; diamond and the like. These fine particles may be used alone or in a combination of two or more in any combination and ratio.

  The reactive diluent is preferably one having two or more epoxy groups in the molecule, and preferably has an epoxy equivalent of 70 g / equivalent or more and 350 g / equivalent or less from the viewpoint of reducing the melt viscosity. More preferably, it is 80 g / equivalent or more and 200 g / equivalent or less. Such reactive diluents include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, Examples thereof include glycidyl ethers of dihydric or higher polyhydric alcohols such as glycerol diglycidyl ether, glycerol triglycidyl ether, and erythritol tetraglycidyl ether.

The resin component is preferably a resin having flexibility and a rubber elastic skeleton, and among them, an epoxy compound having flexibility and a rubber elastic skeleton is particularly preferable.
Further, the rubber-like particles are preferably rubber-like particles having a particle diameter of 0.01 to 1 μm in consideration of suitability for the manufacturing process of the stacked semiconductor device as an interlayer filler. In order to promote dispersibility of the rubber-like particles in the resin, the particle surface may be coated with a resin component different from the rubber-like component. As the rubber-like component, a general-purpose rubber component can be used, and among these, rubber components such as styrene-butadiene rubber, polybutadiene rubber, and silicon rubber are preferable.

  In addition, as an additive component to improve the adhesion to the substrate and the adhesion between the resin and the inorganic filler, coupling agents such as silane coupling agents and titanate coupling agents, UV protection to improve storage stability Thermoplastic oligomers can also be added from the viewpoint of an agent, an antioxidant, a plasticizer, a flame retardant, a colorant, improvement in fluidity during molding and improvement in adhesion to the substrate. Any of these may be used alone or in a combination of two or more in any combination and ratio. There is no restriction | limiting in particular in the compounding quantity of another additive, It is used with the compounding quantity of a normal resin composition to such an extent that required functionality is obtained.

  In the composition of the present invention, in order to reduce elution of ionic components from the cured film and improve the reliability of the stacked semiconductor device, the constituent components are resin, inorganic filler, curing agent, flux, dispersing agent and It is preferable to apply other additives that have been subjected to purification treatment in advance.

  Also, ions that have the action of trapping ion components to reduce the elution of ion components from the cured film and improve the reliability of the stacked semiconductor device when used as an interlayer material of the stacked semiconductor device. It is preferred to use a scavenger. As the ion scavenger, those supplementing alkali metal ions such as sodium ion and potassium potassium ion can be suitably used, but it is more preferable to use a scavenger excellent in capturing halogen ions such as chlorine and bromine, These ion scavengers are preferably inorganic ion exchangers containing bismuth, aluminum, magnesium and the like.

  Further, when the composition of the present invention is used as an interlayer filler for a stacked semiconductor device, if it contains hydrolyzable chlorine, the reliability of the stacked semiconductor device may be lowered. The decomposable chlorine content is preferably 150 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, and particularly preferably 20 ppm or less. In order to make the hydrolyzable chlorine within a preferable range, the hydrolyzable chlorine in the resin (A) is extracted and washed with a solvent such as water, followed by separation or purification by distillation. Can be achieved by applying. For example, 2,2-bis (4-hydroxyphenyl) propane-modified diglycidyl ether is distilled at a temperature of 160 to 200 ° C. under 100 Torr or less, and 1,4-cyclohexanedimethanol diglycidyl ether. The denatured product can be purified by adding pure water, stirring and mixing, allowing to stand and separating the layers, followed by liquid separation and dehydration treatment.

<Laminated semiconductor device>
The laminated semiconductor device of the present invention has a cured product obtained by curing the composition of the present invention between substrates, and silica filler (B) and inorganic filler (E) are added depending on the properties of the resin (A). Even when blended at a high ratio, it exhibits a low melt viscosity and can achieve both high thermal conductivity and solderability.

<Board>
More specifically, the substrate in the stacked semiconductor device of the present invention includes an organic substrate made of epoxy resin or polyimide resin, or a semiconductor substrate on which a wiring circuit, a through electrode (TSV), a semiconductor element circuit, or the like is formed. The layer formed by curing the composition of the present invention may be provided between the organic substrate and the semiconductor substrate, or may be provided between the semiconductor substrate and the semiconductor substrate. It may be provided between the organic substrate. By using the interlayer filler composition of the present invention, even in a laminated semiconductor device composed of an organic substrate and a semiconductor substrate, it is possible to bond a thin semiconductor substrate or a large semiconductor substrate in comparison with conventional interlayer filling by underfill after reflow. Further, it is possible to suppress the warpage of the substrate, suppress the formation of voids even in a large bonding area, and achieve bonding with low resistance between terminals. In addition, the semiconductor substrate has higher surface smoothness than the organic substrate, enables circuit transfer by finer lithography, and enables the formation of smaller connection terminals such as copper posts and solder bumps. By forming the narrow connection terminals between them, it is possible to realize a high performance stacked semiconductor device with higher wiring density.

Organic substrate The organic substrate in the present invention has a conductive wiring circuit, and more specifically, a thermosetting resin such as an epoxy resin or a polyimide resin is formed into a plate shape with a glass fiber interposed therebetween. It is a thing. The linear expansion coefficient of the organic substrate varies depending on the material, but is usually 5 to 50 ppm / K in the case of an organic interposer substrate.
Terminals for connection are provided on the surface of the organic substrate and are usually formed by a combination of a photolithography method and a plating method or a printing method, and the interval between the terminals is usually 50 μm to 300 μm.

-Semiconductor substrate The semiconductor substrate in the present invention includes a semiconductor substrate on which a wiring circuit is formed, a semiconductor substrate on which a through electrode (TSV) is formed, a semiconductor substrate on which a semiconductor element circuit such as a transistor is formed, and silicon. , Germanium, germanium silicide, silicon carbide, gallium arsenide, gallium phosphide, gallium nitride, etc., and a substrate in which phosphorus or boron is doped by ion implantation as required, more specifically, N-type Examples thereof include a silicon substrate and a P-type silicon substrate.
The linear expansion coefficient of the semiconductor substrate is usually 1 to 10 ppm / K, although it varies depending on the material.
Examples of the semiconductor element circuit formed on the surface of the semiconductor substrate include storage elements such as a nonvolatile memory and a dynamic random access memory in addition to arithmetic elements such as a DSP and MPU.

  Since the composition of the present invention has high thermal conductivity, a heat dissipation substrate, a heat dissipation sheet, a heat conductive paste, a heat conductive adhesive, a semiconductor package, a heat sink, heat It can also be used for pipes, casings of electrical and electronic equipment, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited to a following example, unless it deviates from the meaning.
[Composition ingredients]
In the following examples and comparative examples, the blending components used in the compositions are as follows.
<Epoxy compound (a)>
Epoxy compound (a1): Product name “YL6810” manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 171 g / equivalent)
Epoxy compound (a5): Product name “LX-01” manufactured by Daiso Corporation (epoxy equivalent 189 g / equivalent)
Epoxy compound (a6): Mitsubishi Chemical Corporation product name “1006FS” (epoxy equivalent 950 g / equivalent)

<Silica filler (B)>
Silica filler (B1): Silica product name “PLV-4” manufactured by Tatsumori Co., Ltd.
Silica filler (B2): Silica product name “2BV” manufactured by Admatechs Co., Ltd.
<Inorganic filler (E)>
Inorganic filler (E3): Aluminum nitride manufactured by Tokuyama Corporation Product name “Al-H”
Inorganic filler (E6): Sumitomo Chemical Co., Ltd. Alumina Product name “AA-3”
Inorganic filler (E7): Magnesium oxide manufactured by Kamishima Chemical Co., Ltd. Product name “HP-30A”
Inorganic filler (E8): Boron nitride manufactured by Nisshin Rifratech Co., Ltd. Product name “R-BN”
Inorganic filler (E9): Product name “AE-2054SXM” manufactured by Admatechs Co., Ltd.

<Curing agent (C)>
Curing agent (C1): 1-cyanoethyl-2-uredecylimidazole manufactured by Shikoku Kasei Kogyo Co., Ltd. Product name “C11Z-CN”
Curing agent (C2): Polytetramethyleneoxybis-4-aminobenzoate manufactured by Ihara Chemical Industry Co., Ltd. Product name “Elastomer 250P”
Curing agent (C3): 4,4′-diaminodiphenylsulfone manufactured by Wakayama Seika Kogyo Co., Ltd. Product name “Seika Cure S”

<Flux (D)>
Wako Pure Chemical Industries, Ltd. Adipic acid reagent special grade <Dispersant (F)>
Dispersant (F1): BYK-2155 manufactured by Big Chemie Japan KK, amine value (mg-KOH / g) 48

[Evaluation of various physical properties and characteristics]
(1) Melt viscosity of epoxy compound Melt viscosity (parallel plate dynamic viscosity) was measured using a viscoelasticity measuring apparatus Physica MCR102 manufactured by Anton Paar Japan.
First, the epoxy compound to be measured (the composition when a plurality of epoxy compounds are used) was placed between a parallel plate dish and a parallel plate (φ20 mm), and parallel plate dynamic viscosity measurement was performed. .
The measurement conditions were that 20% sinusoidal distortion was applied to the sample, the angular frequency of the distortion was 10 rad / sec, and the viscosity was measured from 40 ° C. to 200 ° C. in the process of raising the temperature at a rate of 3 ° C. per minute.

(2) Particle Size of Silica Filler and Inorganic Filler The composition after stirring and mixing the blending components was dispersed in cyclohexanone, and measured with a particle size distribution analyzer “SALD-2200” manufactured by Shimadzu Corporation. From the obtained particle size distribution, the volume average particle size and the maximum particle size of the pulverized inorganic filler were determined.

(3) Specific surface area of inorganic filler After pretreatment of nitrogen gas flow for 15 minutes at 250 ° C., the inorganic filler was subjected to a BET one-point method (adsorbed gas: nitrogen) using Macsorb HM MODEL-1201 manufactured by Mountec Co., Ltd. The specific surface area was measured.

(4) Crack evaluation What applied 0.1 g of compositions on a 10 mm square silicon substrate (thickness 500 μm),
It hardened | cured at 150 degreeC or 165 degreeC on the hotplate for 2 hours, and cooled to room temperature after the hardening process. At that time, the crack was confirmed by visual inspection, and the cured layer or the silicon substrate that cracked was evaluated as not suitable for use as an interlayer material of the laminated semiconductor device. The product was evaluated to be suitable for use as an interlayer material of a stacked semiconductor device, and “◯” is shown in Table 3.

(5) Thermal conductivity of hardened layer The hardened layer of the composition was determined by measuring the thermal diffusivity, specific gravity, and specific heat using the following apparatus and multiplying these three measured values.
1) Thermal diffusivity: Eye Phase Co., Ltd. “I Phase Mobile 1u”
2) Specific gravity: METTLER TOLEDO Co., Ltd. “Balance XS-204” (Using solid specific gravity measurement kit)
3) Specific heat: Seiko Instruments Inc. “DSC320 / 6200”

(6) Fracture toughness evaluation Fracture toughness evaluation was performed based on ASTM E-399. Using a Shimadzu Corporation MST-I load cell 100N, a three-point bending method was performed at a speed of 0.5 mm / min, and the fracture toughness value was calculated from the maximum load value at the time of fracture. The higher the fracture toughness value, the higher the bonding strength of the semiconductor device, which is preferable. However, when the calculated fracture toughness value is 1.0 (MPa · √m) or more, it is sufficient for use in a stacked semiconductor device. It was evaluated as having strength.

(7) Measurement of glass transition temperature A cured layer of the composition was cut into a size of 20 mm × 3 mm, and a temperature rise rate of 10 ° C./temperature was measured using a Bruker thermomechanical analyzer TMA4000SA with a tension of 5 gf under a nitrogen atmosphere. The displacement (μm) from −50 ° C. to 290 ° C. was measured in min. The intersection of extrapolated lines at points where the slope of the straight line changes greatly was the glass transition point, and the temperature at that time was the glass transition temperature. The higher the glass transition temperature is, the better the heat resistance is, and it is necessary to be higher than the operating temperature of the semiconductor device.

(8) Linear expansion coefficient When measuring the glass transition temperature, the elongation (ppm) of the cured layer per 1 ° C (1K) at -10 ° C to 40 ° C was calculated, and this was calculated as the linear expansion coefficient (ppm / K). did. The composition of the present invention is preferably used between the substrates of the stacked semiconductor device. In that case, the linear expansion coefficient of the cured layer is 20 ppm / K to about the relationship with the linear expansion coefficient of the substrate of the semiconductor device. It is suitable that it is 33 ppm / K.

(9) Evaluation of bondability The prepared composition was applied after applying about 25 μL of a silicon solder bump substrate (CC80ModelI) manufactured by WALTS Co., Ltd. while heating to 80 ° C.
This solder bump substrate and an interposer (IP80Model I) manufactured by WALTS Co., Ltd. were heated up to 250 ° C. using a flip chip bonder (FC3000S) manufactured by Toray Engineering Co., Ltd., and then cured at 150 ° C. for 2 hours after cooling. To form a laminate. The electrical resistance of the daisy chain inside the laminate was measured with a digital multimeter, and those having an electrical resistance of 30Ω or less were deemed acceptable as having been electrically joined, and indicated as “◯” in the table.

(10) Evaluation of voids in the bonding surface For a chip in which a silicon solder bump substrate is bonded to an organic interposer substrate via a composition, an ultrasonic imaging apparatus (HYE-FOC) manufactured by Hitachi Construction Machinery Finetech Co., Ltd.
USII) was used to evaluate the presence or absence of voids between the bumps between the bonded chips. The interlayer material of the stacked semiconductor preferably has few vacancies, and particularly preferably has no vacancies.

[Examples 1 to 4]
The epoxy compound (a1) was weighed into a 125 ml stirring vessel, the dispersant (F1) was added thereto, and the mixture was stirred at 2000 rpm for 5 minutes using a self-revolving stirrer (ARV-310, manufactured by Shinky Corporation). The silica filler (B1), inorganic filler (E6), and inorganic filler (E8) were added in the amounts shown in Table 3, and the mixture was stirred at 2000 rpm for 5 minutes with a revolving stirrer. Further, after adding 6% by weight of the curing agent (C1) to the total resin amount and 2% by weight of the flux (D) based on the total resin amount, 5% at 2000 rpm 1.2 kPa with a revolutionary agitator. Stirring was performed while degassing under reduced pressure for minutes to obtain compositions of Examples 1 to 4. Table 1 shows the physical properties of the epoxy compound used, and Table 2 shows the volume average particle diameter and specific surface area of the filler.

  Each of these compositions was applied onto a release film placed on a glass substrate, and the release film and the glass substrate were further placed on the coating layer via a spacer, and then pressed at 150 ° C. for 2 hours. (Pressure of 1 MPa) was formed and cured to form a layer having a thickness of 500 μm. Table 3 shows the linear expansion coefficient and thermal conductivity of these layers.

  After 0.1 g of the composition of Example 2 was applied on a 10 mm square silicon substrate (film thickness 500 μm) at 80 ° C., it was cured on a hot plate at 150 ° C. for 2 hours. After completion of the curing reaction, the silicon substrate was cooled to room temperature, and no cracks were generated in the layer made of the composition and the silicon substrate.

Using the compositions of Example 2 and Example 4, about 25 μL of these compositions were applied to a silicon solder bump substrate (CC80ModelI) manufactured by WALTS Co., Ltd. while heating at 80 ° C. This was heated up to 250 ° C. using an interposer (IP80Model I) manufactured by WALTS Co., Ltd. and a flip chip bonder (FC3000S) manufactured by Toray Engineering Co., Ltd., and then cured at 150 ° C. for 2 hours after cooling. A laminate was formed. When the electric resistance of the daisy chain inside the laminate was measured with a digital multimeter, all the samples were good at 30Ω or less.
When these laminates were observed for the presence or absence of voids between the bumps between the bonding chips using an ultrasonic imaging apparatus (HYE-FOCUSII) manufactured by Hitachi Construction Machinery Finetech Co., Ltd. No voids were found in the sample, and the sample was well bonded.

[Examples 5 to 13]
As shown in Table 3, the epoxy compound (a5) was weighed into a 125 ml stirring vessel, and the curing agents (C2) and (C3) were added thereto, and further the dispersing agent (F1) was added. The mixture was stirred at 2000 rpm for 5 minutes using a revolutionary stirrer (ARV-310, manufactured by Shinky Corporation). To this, silica filler (B1) or (B2) and inorganic fillers (E3), (E6), (E7) and (E8) were added in amounts as shown in Table 3, and 2000 rpm with a revolving stirrer. For 5 minutes. Furthermore, after adding 1% by weight of the flux (D) to the total resin amount, the mixture was stirred while being degassed under reduced pressure at 2000 rpm 1.2 kPa for 5 minutes with a self-revolving stirrer. I got a thing. Table 1 shows the physical properties of the epoxy compound used, and Table 2 shows the volume average particle diameter and specific surface area of the filler.

In the same manner as in Examples 1 to 4, these compositions were molded and cured to form a layer having a thickness of 500 μm. Table 3 shows the linear expansion coefficient and thermal conductivity of these layers.
The composition of Example 6 and Example 10 is a 10 mm square silicon substrate (film thickness 500 μm).
After coating 0.1 g at 80 ° C. on the top, it was cured on a hot plate at 165 ° C. for 2 hours. After completion of the curing reaction, the silicon substrate was cooled to room temperature. As a result, neither the cured layer of the composition nor the silicon substrate was cracked.

Using the compositions of Example 6, Example 10, and Example 11, bonding was performed in the same manner as in Example 2 to form a laminate. The electrical resistance of the daisy chain inside the laminate was measured with a digital multimeter and found to be good at 20Ω or less.
When this laminate was observed for the presence of voids between the bumps between the bonding chips using an ultrasonic imaging device (HYE-FOCUSII) manufactured by Hitachi Construction Machinery Finetech Co., Ltd. It was not able to be joined well.

  When the fracture toughness of the compositions of Example 10 and Example 11 was evaluated, the fracture toughness of the sample obtained from the composition of Example 10 was 1.8, which was sufficient as a stacked semiconductor device. It was a pass. Further, the sample obtained from the composition of Example 11 had a fracture toughness of 2.2, which had a higher preferable toughness and passed.

[Comparative Examples 1 and 2]
In Comparative Example 1, only the silica filler (B1) was used as the filler, and in Comparative Example 2, only the inorganic filler (E6) was used. The layers were formed in the same manner as in Examples 1 to 4 except that the amounts shown in Table 3 were used. . Table 3 shows the results of linear expansion coefficient and thermal conductivity of this layer.
In the same manner as in Example 2, 0.1 g of the composition of Comparative Example 2 was applied on a 10 mm square silicon substrate (film thickness 500 μm) at 80 ° C., and then cured on a hot plate at 150 ° C. for 2 hours. After the curing reaction, when the silicon substrate was cooled to room temperature, a large crack was generated in the silicon substrate.

[Comparative Example 3]
In Comparative Example 3, the same procedure as in Examples 1 to 4 was carried out except that the amount of the epoxy compound (a6) was changed to that shown in Table 3. After adding the filler (B) and the inorganic filler (E6), the mixture was stirred for 5 minutes at 2000 rpm with a revolving stirrer, but the resin and the filler could not be uniformly stirred and mixed.

  According to the present invention, it is possible to form a high-quality interlayer filling layer having high thermal conductivity without causing cracks at the same time as bonding of solder bumps between semiconductor device substrates and lands.

Claims (17)

  Contains a resin (A) having a melt viscosity at 120 ° C. of 0.001 to 1 Pa · s, a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and an inorganic filler (E) that is not silica. Composition.   The composition according to claim 1, wherein the inorganic filler (E) has a volume average particle size of 0.1 μm or more and 10 μm or less.   The composition of Claim 1 or Claim 2 whose difference of the volume average particle diameter of the said silica filler (B) and an inorganic filler (E) is 1 micrometer or more and 5 micrometers or less. The specific surface area of the silica filler (B) is less than or equal to 0.1 m ² / g or more 100 m ² / g, the composition according to any one of claims 1 to 3. The specific surface area of the inorganic filler (E) is at 0.1 m ² / g or more ^{20 m} 2 / g or less, the composition as claimed in any one of claims 4.   The composition according to any one of claims 1 to 5, wherein a content of the silica filler (B) is 40 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the resin (A). .   The composition according to any one of claims 1 to 6, wherein the resin (A) is a thermosetting resin.   The composition according to any one of claims 1 to 7, wherein the resin (A) is an epoxy compound (a).   The composition according to claim 8, wherein the epoxy compound (a) comprises an epoxy compound (a-1) having an epoxy equivalent of 150 g / equivalent to 650 g / equivalent.   The composition according to claim 8 or 9, further comprising a curing agent (C).   The composition according to any one of claims 1 to 10, further comprising a flux (D).   Contains a resin (A) having a melt viscosity at 120 ° C. of 0.001 to 1 Pa · s, a silica filler (B) having a volume average particle size of 0.1 μm to 10 μm, and an inorganic filler (E) that is not silica. A method for producing a composition comprising: mixing at least two of all components under a temperature condition of 40 ° C to 160 ° C.   The method for producing a composition according to claim 12, wherein at least two of all components are mixed under a pressure condition of 100 Torr or less.   A layer made of the composition according to any one of claims 1 to 11 is formed on a surface of a semiconductor substrate by a pre-apply method, and the semiconductor substrate and another substrate are laminated and heat-press bonded. The manufacturing method of a laminated semiconductor device including the process processed at 50 to 200 degreeC.   The method for manufacturing a stacked semiconductor device according to claim 14, wherein the other substrate is a semiconductor substrate.   16. The method for manufacturing a stacked semiconductor device according to claim 14, wherein at least one of the semiconductor substrates is a semiconductor substrate having a semiconductor circuit element.   12. A stacked semiconductor device in which at least two semiconductor substrates each having a semiconductor circuit element are stacked, wherein at least one of the semiconductor substrates includes an interlayer filler according to claim 1. A stacked semiconductor device having a layer formed by curing a composition.