TW201625708A - Method for making semiconductor device - Google Patents

Abstract

Provided is a method for making a semiconductor device wherein a cured adhesive layer that is excellent in bonding property and in conductivity can be formed without occurrence of voids in the cured adhesive layer. In a method for making a semiconductor device by using thermocompression bonding equipment to thermocompression-bond together a semiconductor chip having solder bumps and a semiconductor board having electrode pads with an interlayer filler composition intervening therebetween, the bonding is performed on temperature condition that the temperatures of the head and stage of the thermocompression bonding equipment are in a range defined, in a graph having an ordinate axis representative of the head temperature and having an abscissa axis representative of the stage temperature, by the following four equations: H + 1.9S = 590 Equation 1, H + 0.526S = 310 Equation 2, H + 0.8S = 580 Equation 3, H + 1.25S = 725 Equation 4, where H is the head temperature (centigrade) and S is the stage temperature (centigrade).

Description

Semiconductor component manufacturing method

The present invention relates to a method of manufacturing a semiconductor element by thermally bonding a semiconductor wafer having a solder bump and a semiconductor substrate having an electrode pad via an interlayer filler composition by a thermocompression bonding apparatus.

In order to further improve the performance of the semiconductor device, in addition to the miniaturization of the transistor or the wiring, a plurality of substrates such as a semiconductor substrate or an organic substrate on which the semiconductor element layer is formed are stacked, and the substrate faces are vertically stacked and laminated. Research and development of laminated semiconductor devices.

In the laminated semiconductor device, a semiconductor substrate and an organic substrate are known. More specifically, it is known that semiconductor substrates are connected to each other by electrical signal terminals such as solder bumps between the substrates, and are filled between the substrates. An interlayer filler composition is a three-dimensional laminated semiconductor device having a structure in which a substrate is adhered to each other by an interlayer filler composition layer.

As a method of manufacturing a stacked-type semiconductor device, it is proposed to form a layer composed of an interlayer filler composition (ICF: Inter Chip Fill) on a wafer on which a semiconductor element layer is formed, and to perform step-by-step heating as needed. Next, wafer cutting is performed by dicing, and the obtained semiconductor substrate is laminated in plural layers, and the temporary bonding by pressurization heating is repeated, and finally a pre-applied process of performing the final bonding under pressurized heating conditions (for example, Reference is made to Non-Patent Document 1).

2 is a view showing the manufacture of a semiconductor device by a pre-method. A perspective view of the method; on the semiconductor wafer 2 on which the plurality of solder bumps 1 composed of the pad terminal 1A and the solder 1B are formed, the interlayer filler composition 3 is supplied from the coating nozzle 4 (Fig. 2(a)) to form After the interlayer filler composition layer 5 (Fig. 2(b)), B-stage is performed as needed, and the semiconductor wafer 2 on which the interlayer filler composition layer 5 is formed is inverted, and placed on the thermocompression bonding apparatus. On the platform (not shown), the semiconductor substrate 7 on which the electrode pads 6 are formed is placed on the side of the interlayer filler composition layer 5, and is pressed by an indenter (not shown) (Fig. 2(c)). The semiconductor substrate 7 and the semiconductor wafer 2 are heated and pressurized between the indenter and the platform of the thermocompression bonding device, thereby hardening the interlayer filler composition layer, thereby obtaining hardening adhesion through the interlayer filler composition. The layer 8 is a semiconductor element 10 in which the semiconductor wafer 2 is bonded to the semiconductor substrate 7 (Fig. 2(d)).

In the laminated semiconductor device, the semiconductor wafer 2 of the semiconductor device 10 shown in FIG. 2(d) is repeated (in this case, an electrode pad is formed on the surface of the semiconductor wafer 2 opposite to the hardened adhesive layer 8). Further, the semiconductor wafer 2 on which the interlayer filler composition layer 5 is formed as shown in Fig. 2(b) is further bonded, and this step is repeated to manufacture.

[Previous Technical Literature] [Non-patent literature]

Non-Patent Document 1: Electronics Installation Society Lectures (61-62, 23rd, 2009)

In the manufacture of the semiconductor device of the pre-method, there are the following problems.

(1) A void is formed in the hardened adhesive layer. The occurrence of voids is considered to be due to the low molecular component of the interlayer filler composition under the heating conditions of the bonding step or the hardening step. Volatilization is the cause. If there is a void in the hardened adhesive layer, not only the electrical joint is damaged, but the shrinkage difference such as temperature change becomes large, and the adhesive surface is peeled off or broken, thereby impairing the performance of the semiconductor device.

(2) As shown in FIG. 2(a), when the interlayer filler composition 3 is supplied onto the semiconductor wafer 2 on which the solder bumps 1 are formed to form the interlayer filler composition layer, since the interlayer filler composition 3 is not The gap between the solder bumps 1 and 1 is sufficiently spread, and the void portion of the void is formed in the same manner as in the above (1), and the same problem as described above occurs.

As described above, it is desirable that a void is formed in the hardened adhesive layer between the semiconductor wafer-substrate or the semiconductor wafer-semiconductor wafer, and a cured adhesive layer having excellent adhesion and conductivity is formed.

An object of the present invention is to provide a bond between a semiconductor wafer-substrate or a semiconductor wafer-semiconductor wafer in the production of a semiconductor device, and voids are formed in the cured adhesive layer, and the bonding property and the conductive property are excellent. A method of manufacturing a high-quality and highly reliable semiconductor device by hardening an adhesive layer.

The present inventors have diligently studied in order to solve the above problems, and as a result, have found that the above problems can be solved, and the present invention is completely invented.

That is, the gist of the present invention is as follows.

[1] A method of manufacturing a semiconductor device, wherein a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad are thermally bonded by a thermocompression bonding device via an interlayer filler composition to fabricate a semiconductor device. The temperature of the indenter and the platform of the thermocompression bonding apparatus is in a graph in which the head temperature is the vertical axis and the platform temperature is the horizontal axis, and is within the range surrounded by the following four equations. Temperature condition Engagement; H+1.9S=590...Formula 1 H+0.526S=310...Formula 2 H+0.8S=580...Formula 3 H+1.25S=725...Formula 4 (in Equations 1-4, H represents the time of bonding) Indenter temperature (°C), S indicates the platform temperature (°C) at the time of bonding).

[2] A method of manufacturing a semiconductor device, comprising: a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad, and an interlayer bonding by means of a thermocompression bonding device having an indenter and a stage which can be individually temperature-adjusted The composition of the composition is thermocompression bonded to produce a semiconductor component; the temperature of the indenter and the platform of the thermocompression bonding device is in a graph in which the temperature of the indenter is the vertical axis and the temperature of the platform is the horizontal axis. It is joined by temperature conditions in the range surrounded by the following four formulas; H + 1.9S = 590... Formula 1 H + 0.526S = 310... Formula 2 H + 0.8S = 580... Equation 3 H + 1.25S = 725... Formula 4 (in the formulas 1 to 4, H represents the head temperature (°C) at the time of joining, and S represents the stage temperature (°C) at the time of joining).

[3] The method for producing a semiconductor device according to the above [1] or [2] wherein the interlayer filler composition has a viscosity at 130 ° C of 100 Pa ‧ or less.

[4] The method of manufacturing a semiconductor device according to any one of the above [1] to [3] wherein The interlayer filler composition contains an epoxy resin (A), a hardener (B), a filler (C), and a flux (D).

[5] The method for producing a semiconductor device according to the above [4], wherein the interlayer filler composition further contains a curing accelerator (E).

[6] The method for producing a semiconductor device according to the above [4] or [5] wherein the interlayer filler composition further contains a dispersant (F).

[7] The method for producing a semiconductor device according to any one of [4] to [6] wherein the curing agent (B) is 30 to 150 parts by weight per 100 parts by weight of the epoxy resin (A). .

[8] The method for producing a semiconductor device according to any one of the above [4], wherein the curing agent (B) contains at least one curing agent selected from the group consisting of an amine curing agent and an acid anhydride curing agent.

[9] The method for producing a semiconductor device according to the above [8], wherein the hardener (B) is based on an equivalent ratio of the functional group in the hardener (B) to the epoxy group in the epoxy resin (A). It is in the range of 0.8~1.5.

[10] A method of manufacturing a semiconductor device, comprising: a step of bonding a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad via an interlayer filler composition using a thermocompression bonding apparatus; The temperature of any one of the indenter or the platform of the adhesive bonding device is 120 ° C or higher, the solder bump is brought into contact with the electrode pad, and after the solder bump is in contact with the electrode pad, the indenter or the platform is applied to the solder bump. The temperature at the side less than 120 ° C when the block is in contact with the electrode pad becomes the melting point of the solder.

[11] The method of manufacturing a semiconductor device according to the above [10], wherein the semiconductor crystal is disposed on a side of the indenter or the platform which is less than 120 ° C when the solder bump is in contact with the electrode pad. The sheet or the semiconductor substrate is bonded by applying the interlayer filler composition in advance.

[12] The method for producing a semiconductor device according to the above [10] or [11] wherein the interlayer filler composition has a viscosity at 100 ° C of 0.1 to 10 Pa ‧ s.

[13] The method for producing a semiconductor device according to the above [11] or [12] wherein the interlayer filler composition contains an epoxy resin (A), a hardener (B), a filler (C), and a flux ( D).

[14] The method for producing a semiconductor device according to the above [13], wherein the interlayer filler composition contains a curing accelerator (E).

According to the present invention, in the manufacture of a semiconductor element, in the bonding between the semiconductor wafer-substrate or the semiconductor wafer-semiconductor wafer, the hardened adhesive layer does not have voids, and the bonding and the conductivity are excellent. By bonding the adhesive layer, it is possible to manufacture a semiconductor component of high quality and excellent reliability.

According to the present invention, it is possible to achieve further high speed and high capacity of the laminated semiconductor device.

1‧‧‧ solder bumps

1A‧‧‧pad terminal

1B‧‧‧ solder

2‧‧‧Semiconductor wafer

3‧‧‧Interlayer filler composition

4‧‧‧ Coating nozzle

5‧‧‧Interlayer filler composition layer

6‧‧‧electrode pads

7‧‧‧Semiconductor substrate

8‧‧‧ hardened adhesive layer

10‧‧‧Semiconductor components

11‧‧‧through electrode (TSV)

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the temperature regions of the indenter and the platform at the time of joining of the present invention.

2 is a perspective view showing a method of manufacturing a semiconductor device of a front method. Fig. 2(a) is a view showing the operation of a filler composition between coating layers in a semiconductor wafer. Fig. 2(b) is a view showing a semiconductor wafer having an interlayer filler composition layer. 2(c) is a view showing an operation of heat-and-pressure bonding a semiconductor wafer having a layer of an interlayer filler composition by a thermocompression bonding apparatus (not shown) on a semiconductor substrate. Figure 2 (d) is a half of a semiconductor wafer bonded to a semiconductor substrate via a hardened adhesive layer of an interlayer filler composition A diagram of a conductor element.

Fig. 3(a) is a photograph showing the appearance of the semiconductor device produced in the twenty-fifth embodiment; Fig. 3(b) is a cross-sectional photograph of the same.

The embodiments of the present invention are described below, but the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

Hereinafter, in the method of manufacturing a semiconductor device of the present invention, an interlayer filler composition for bonding a semiconductor wafer having solder bumps to a semiconductor substrate having an electrode pad may be referred to as an "interlayer filler composition". "." Further, the "semiconductor wafer" and the "semiconductor substrate" of the present invention may be collectively referred to as "substrate". The semiconductor wafer and the semiconductor substrate are generally formed of any material used as a substrate for a semiconductor in the manufacture of an integrated circuit, and a substrate on which a solder bump is formed is referred to as a "semiconductor wafer", and an electrode bonded to the solder bump is formed. The pad is called a "semiconductor substrate." A through electrode (hereinafter sometimes abbreviated as TSV) or a semiconductor element circuit may be formed on the semiconductor wafer and the semiconductor substrate, and the substrate may be connected to the electrode pad via a solder bump.

Further, in the case of using a substrate having solder bumps and electrode pads on the same substrate, the substrate may be a semiconductor wafer or a semiconductor substrate. However, one substrate is not simultaneously configured as a "semiconductor wafer" or a "semiconductor substrate".

[Method of Manufacturing Semiconductor Element]

First, a method of manufacturing the semiconductor device of the present invention will be described. The interlayer filler composition will be described later.

The method of manufacturing a semiconductor device of the present invention uses thermocompression bonding The device heat-pressurizes the semiconductor wafer having the solder bumps and the semiconductor substrate having the electrode pads via an interlayer filler composition described later; the temperature of the indenter and the platform of the thermocompression bonding device is as shown in FIG. In the graph in which the head temperature is the vertical axis and the platform temperature is the horizontal axis, the bonding is performed under the temperature conditions in the range surrounded by the following four equations. Here, the temperature of the indenter refers to the temperature of the heater of the indenter of the thermocompression bonding device, and the temperature of the platform refers to the temperature of the heater of the platform of the thermocompression bonding device.

H+1.9S=590...Form 1

H+0.526S=310...Form 2

H+0.8S=580...Form 3

H+1.25S=725...4

In the above formulas 1 to 4, H represents the head temperature (°C) at the time of joining, and S represents the stage temperature (°C) at the time of joining.

In the present invention, the temperature of the indenter and the stage of the thermocompression bonding apparatus are individually adjusted, and the bonding is performed under the temperature conditions in the range surrounded by the above four equations. Therefore, a method of joining the substrate to be bonded to a furnace represented by a high-temperature bath or the like and heating the whole is different. Among them, the results of individual temperature adjustments did not rule out that the temperature of the indenter and the platform were the same. As the thermocompression bonding apparatus having the indenter and the stage which can be individually temperature-adjusted, the Flip Chip Bonder (FC3000S) manufactured by Toray Engineering Co., Ltd., which is used in the later-described embodiment, can be used.

The temperature of the indenter and the platform for individual temperature adjustment is based on the reason that the time required for such temperature rise can be shortened to increase the production efficiency or reduce the energy required for the temperature rise, and it is preferred that the temperature of either one is lower than the other. . As a result, it is preferred that the temperature of the press head differs from the temperature of the stage.

According to the present invention, by bonding in the temperature region surrounded by the above formulas 1 to 4, occurrence of voids in the cured adhesive layer can be suppressed, and the semiconductor wafer having the solder bumps and the semiconductor substrate having the electrode pads can be bonded well. Sexuality and continuity are joined. Outside of the temperature range surrounded by Formulas 1 to 4, voids are generated and the bondability is also deteriorated.

In the temperature range surrounded by the above formulas 1 to 4, a more preferable temperature region is surrounded by the following formulas 5 to 8, and the particularly preferable temperature region is surrounded by the following formulas 5 to 8. Inside.

H+1.774S=624... Equation 5

H+0.564S=352...Form 6

H+0.72S=550... Equation 7

H+1.39S=764...8

In the present invention, when the bonding is performed by the thermocompression bonding apparatus, the above temperature conditions may be employed. However, in order to fully exert the functions required for the interlayer material, the stage temperature is preferably 70 to 500 ° C, more preferably 100 to 450 ° C. Further preferably 120 to 430 ° C; the head temperature is preferably 70 to 500 ° C, more preferably 100 to 450 ° C, and even more preferably 120 to 430 ° C. Further, in terms of electrical bonding, the temperature of the indenter and the stage is preferably higher than a certain level, and preferably at least one of them is higher than 225 ° C, more preferably 230 ° C or higher, and particularly preferably 235 ° C or higher.

The pressing force in the joining step according to the above specific temperature conditions is 0.1 to 50 Kgf/cm ² and particularly preferably 0.1 to 10 Kgf/cm ² . The heating and pressing time is set to 0.1 to 30 seconds, and particularly preferably 0.5 to 10 seconds.

Further, after the heat and pressure bonding by the thermocompression bonding device, the device may be temporarily removed by the device, cooled to room temperature, and then heated to a hardening position of 100 to 200 ° C. Reason.

In the method for manufacturing a semiconductor device of the present invention, in addition to individually adjusting the temperature of the indenter and the stage of the thermocompression bonding apparatus, a semiconductor wafer having solder bumps and a semiconductor having an electrode pad can be subjected to a usual method in addition to the above temperature conditions. Bonding of the substrate. For example, as shown in FIG. 2(a), the semiconductor substrate (semiconductor wafer) 2 on which the plurality of solder bumps 1 composed of the pad terminal 1A and the solder 1B are formed is supplied to the present invention by the application nozzle 4. As shown in FIG. 2(b), the interlayer filler composition 3 is formed into an interlayer filler composition layer 5, and then B-staged as necessary. Thereafter, the semiconductor wafer 2 on which the interlayer filler composition layer 5 is formed is vertically inverted, and as shown in FIG. 2(c), is formed on a platform (not shown) of the thermocompression bonding apparatus. On the semiconductor substrate 7 of the electrode pad 6, the interlayer filler composition layer 5 side is opposed to each other, and is pressed by a embossing head (not shown). The semiconductor substrate 7 and the semiconductor wafer 2 are heated and pressurized according to the above temperature conditions between the indenter of the thermocompression bonding apparatus and the stage, thereby hardening the interlayer filler composition as shown in FIG. 2(d). The semiconductor element 10 in which the semiconductor wafer 2 and the semiconductor substrate 7 are bonded via the hardened adhesive layer 8 of the interlayer filler composition is obtained.

The laminated semiconductor device having a plurality of semiconductor wafers 2 is repeated in the semiconductor wafer 2 of the semiconductor device 10 shown in FIG. 2(d) (at this time, the semiconductor wafer 2 and the hardened adhesive layer 8 are The semiconductor wafer 2 on which the interlayer filler composition layer 5 is formed as shown in Fig. 2(b) is further bonded to the electrode pad on the opposite side, and this step can be repeated. At this time, the bonded first semiconductor wafer and the second semiconductor wafer further laminated thereon are regarded as the semiconductor substrate of the present invention, and the second semiconductor wafer is regarded as the semiconductor wafer of the present invention. .

The semiconductor wafer and the semiconductor substrate in the present invention are generally usable by In the manufacture of an integrated circuit, a substrate made of any material as a substrate for a semiconductor can be used. Among them, it is preferred to use a tantalum substrate. The tantalum substrate can be used as it is, and can be used by back-graining such as backside etching or back grinding, and can be used to form a film thickness of 100 μm or less.

A fine solder ball may be used for forming the solder bump, or after the opening is formed by photolithography, solder plating may be performed directly on the base of the opening or after forming a pillar of nickel or copper to remove the solder resist. Thereafter, solder bumps are formed by heat treatment. The composition of the solder is not particularly limited, and it is preferable to use solder containing tin as a main component after considering electrical bonding properties and low-temperature bonding properties.

The pad terminal is formed by forming a thin film on a substrate using PVD (Physical Vapor Deposition) or the like, and then forming a thin film by photolithography and dry-type wet etching to remove unnecessary portions. The material of the pad terminal is not particularly limited as long as it can be bonded to the solder bump, and it is preferable to use gold, copper, nickel or the like in consideration of the bonding property and reliability between the solders.

The interlayer filler composition layer obtained by the pre-formation method can be formed by a conventional formation method such as dip coating method, spin coating method, spray coating method, knife coating method, or any other method. The interlayer filler composition layer may be formed on the side of the semiconductor wafer 2 having the solder bumps as shown in FIG. 2, or may be formed on the side of the semiconductor substrate 7 having the electrode pads as in the embodiment described later, or may be formed. These two parties.

The amount of the interlayer filler composition to be supplied to the semiconductor wafer is 1 to 50 mg/cm ² and particularly preferably 2 to 30 mg/cm ² per unit area of the semiconductor wafer. When the interlayer filler composition is supplied to the semiconductor substrate side or the interlayer filler composition is supplied to both the semiconductor wafer and the semiconductor substrate to form an interlayer filler composition layer, the coating amount is applied to such a degree. The inter-layer filler composition can be used.

After the interlayer filler composition layer is formed on the semiconductor wafer (and/or the semiconductor substrate), the low molecular weight component or the like contained in the interlayer filler composition may be removed at any temperature of 50 to 150 ° C, preferably 60. Baking treatment is carried out at any temperature of ~130 ° C for B-stage treatment.

At this time, the baking treatment may be performed at a constant temperature, but in order to smoothly remove the volatile component in the composition, the baking treatment may be performed under reduced pressure. Further, the baking treatment may be carried out in a stepwise temperature rise in a range in which the resin hardening is not performed. For example, baking treatment of about 5 to 90 minutes may be carried out first at 60 ° C, then 80 ° C, and then 120 ° C.

In the method of manufacturing a semiconductor device having a step of bonding a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad via an interlayer filler composition and using a thermocompression bonding apparatus, the bonding method is as described in the present invention. The conditions of the various steps of the previous stage are also of independent importance for the manufacture of high quality semiconductor components. Of course, in the case where both the conditions of the step of bonding using the thermocompression bonding apparatus or the conditions of each step of the pre-bonding stage are preferable, a particularly high-quality semiconductor element can be manufactured.

More specifically, the solder bumps are in contact with the electrode pads in the stage before the heat-and-pressure bonding, but in the case of contact, it is preferably any one of the indenters or the platforms of the thermocompression bonding device. The solder bump is brought into contact with the electrode pad in a state where the temperature is 120 ° C or higher. Further, after the contact, the temperature of the indenter or the platform on the side less than 120 ° C when the solder bump is in contact with the electrode pad is preferably a temperature condition equal to or higher than the melting point of the solder, and the heating and pressure bonding is performed. . At this time, it is more preferable to apply the interlayer filler composition in advance to the wafer or substrate provided on the side where the solder bumps are not more than 120 ° C when the electrode pads are brought into contact. At this time, if the viscosity of the interlayer filler composition is too high, it becomes heated. In the case of hindrance at the time of press bonding, the temperature on the side less than 120 ° C when the solder bump and the electrode pad are in contact with each other is preferably 40 ° C or higher.

Alternatively, after the interlayer filler composition layer is formed, the semiconductor wafer to be bonded and the semiconductor wafer and/or the semiconductor substrate may be dummy bonded. The temperature of the dummy joint is preferably from 80 ° C to 150 ° C. In the case where the bonding is a plurality of layers, the dummy bonding may be repeated depending on the number of substrate layers, or after the plurality of layers are stacked on the substrate, heating may be performed to perform dummy bonding. In the case of dummy bonding, it is preferably carried out by applying a load of ¹ gf/cm ² to 50 Kgf/cm ² , more preferably 10 gf/cm ² to 10 Kgf/cm ² between the substrates as needed.

[Interlayer filler composition]

The interlayer filler composition of the present invention preferably contains an epoxy resin (A), a curing agent (B), a filler (C), and a flux (D), and has a viscosity at 130 ° C (hereinafter sometimes referred to as "η" ₁₃₀ ") is preferably 100 Pa‧s or less.

The interlayer filler composition of the present invention preferably further contains a hardening accelerator (E) and a dispersing agent (F).

[viscosity]

The interlayer filler composition of the present invention preferably has a viscosity η ₁₃₀ at 130 ° C of a low viscosity of 100 Pa ‧ or less. When the η _{130 of the} interlayer filler composition is higher than 100 Pa ‧ s, the interlayer filler composition does not easily flow during bonding, and joint failure may occur. The η _{130 of the} interlayer filler composition of the present invention is _more preferably 50 Pa‧s or less, and particularly preferably 10 Pa‧s or less. Among them, if the viscosity is too low, it is difficult to form Fillet Formation, and therefore the η _{130 of the} interlayer filler composition of the present invention is preferably 0.1 Pa ‧ or more.

In order to modulate the interlayer filler composition of such viscosity, if low viscosity is used The epoxy resin (A) contained in the interlayer filler composition or the adjustment curing agent (B) or other components may be blended.

Further, in the present invention, the viscosity of the interlayer filler composition is a value measured by the method described in the following examples.

[Epoxy Resin (A)]

The epoxy resin (A) used in the present invention is preferably a compound having two or more epoxy groups in order to increase the glass transition temperature of the interlayer filler composition of the present invention. In addition, in order to set the value of the fracture toughness value K1c of the cured product obtained by thermally curing the interlayer filler composition of the present invention to be high, the range of the epoxy group contained in one molecule is preferably 1 or more and 8 The following is more preferably 2 or more and 3 or less.

In order to enhance the thermal conductivity of the interlayer filler composition of the present invention, the epoxy resin (A) used in the present invention is preferably a bisphenol A type skeleton, a bisphenol F type skeleton, or a biphenyl skeleton. An aromatic ring epoxy compound.

More specifically, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, a naphthalene ring-containing epoxy resin, and a dicyclopentane can be exemplified. Diene skeleton epoxy resin, phenol novolak type resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, aliphatic epoxy resin, aliphatic epoxy resin and aromatic ring An epoxy resin copolymerized epoxy resin or the like. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin or epoxy resin containing a naphthalene ring is preferable. A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene ring-containing epoxy resin or a biphenyl type epoxy resin is used.

Moreover, in order to improve the hardening of the interlayer filler composition by heat hardening As the fracture toughness of the compound, a polyfunctional epoxy resin is also used as the epoxy resin (A) used in the present invention.

As the polyfunctional epoxy resin, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolac resin, a dicyclopentadiene phenol resin, a phenol aralkyl resin, a naphthol novolac resin, a biphenol is preferable. a phenol such as an aldehyde varnish resin, a phenol resin, a heavy oil-modified phenol resin, or a polyvalent phenol resin obtained by a condensation reaction of a phenol with an aldehyde such as hydroxybenzaldehyde, crotonaldehyde or glyoxal Each of the phenolic compounds and a glycidyl ether type polyfunctional epoxy resin such as an epoxy resin produced from epichlorohydrin.

These epoxy resins (A) may be used singly or in combination of two or more kinds in any combination and in any ratio.

[hardener (B)]

The curing agent (B) used in the present invention is a substance which contributes to the crosslinking reaction between the crosslinking groups of the epoxy resin (A).

The curing agent (B) is not particularly limited, and a generally known epoxy resin curing agent can be used. For example, an amine-based curing agent such as a phenolic curing agent, an aliphatic amine, a polyetheramine, an alicyclic amine or an aromatic amine, an acid anhydride-based curing agent, a guanamine-based curing agent, a tertiary amine, an imidazole or a derivative thereof may be mentioned. A compound, an organic phosphine, a phosphonium salt, a tetraphenylboronium salt, an organic acid diterpene, a boron halide amine complex, a polythiol-based curing agent, an isocyanate-based curing agent, a blocked isocyanate-based curing agent, and the like.

Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, and 1,4-bis (4). -hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4 '-Dihydroxydiphenyl hydrazine, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxyl linkage Benzene, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, Cresol novolac, p-cresol novolac, xylenol varnish, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, tert-butylcatechol, tert-butyl hydroquinone, fluorine Ethanolamine, gallic phenol, tert-butyl gallophenol, allylated quinopolol, polyallylated pentapeptide, 1,2,4-benzenetriol, 2,3,4-trihydroxydiphenyl ketone, 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-dihydroxynaphthalene, 2,8- Dihydroxynaphthalene, allylate or polyallyl of dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated quinol Wait.

Examples of the aliphatic amines belonging to the amine-based curing agent include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, and 2,5-dimethyl group. Hexamethylenediamine, trimethylhexamethylenediamine, diethylidenetriamine, iminodipropylamine, bis(hexamethylene)triamine, tris-ethyltetramine, tetrazide Pentylamine, pentaethylhexamine, N-hydroxyethylethylenediamine, tetrakis(hydroxyethyl)ethylenediamine, and the like. The polyetheramines may, for example, be triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine or polyoxypropylene triamine. As the alicyclic amines, isophorone diamine, menthane diamine, and N-aminoethyl pipe can be exemplified. , bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10 - tetraoxaspiro (5,5) undecane, descending Ene diamine and the like. Examples of the aromatic amines include tetrachloro-p-xylylenediamine, m-xylenediamine, p-xylenediamine, meta-phenylenediamine, o-phenylenediamine, and p-phenylenediamine. , 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'- Diamino-1,2-diphenylethane, 2,4-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, m-aminophenol, m-aminobenzylamine , benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl) Ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, and the like.

Specific examples of the acid anhydride-based curing agent include dodecenyl succinic anhydride, polyadipate anhydride, polysebacic anhydride, polysebacic anhydride, poly(ethyl octadecandioic acid) anhydride, and poly(phenyl). Hexadecanedioic acid anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicycloheptylene anhydride, tetrahydrophthalic anhydride, three Alkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic anhydride, B Glycol trimellitic acid dianhydride, chloro-bromic anhydride, nadic anhydride, methyl acid anhydride, 5-(2,5-di-s-oxytetrahydro-3-furanyl)-3- Methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-di Carboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1 - Naphthyl succinic dianhydride or the like.

The amide-based curing agent may, for example, be dicyanodiamine or a polyamide resin.

As the tertiary amine, 1,8-diazabicyclo(5,4,0)undecene-7, tri-ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Ginseng (dimethylaminomethyl) phenol and the like.

As the imidazole or a derivative thereof, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methyl can be exemplified Imidazole, 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-all three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, or an adduct of an epoxy resin and the above imidazoles, and the like.

The organic phosphines may, for example, be tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine or phenylphosphine. The onium salt may, for example, be tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium, ethyltriphenylborate or tetrabutylphosphonium tetrabutylborate. As the tetraphenylboron salt, 2-ethyl-4-methylimidazole‧tetraphenylborate and N-methyl can be exemplified Porphyrin ‧ tetraphenyl borate and the like.

These curing agents (B) may be used singly or in combination of two or more kinds in any combination and in any ratio.

The content of the hardener (B) in the interlayer filler composition is preferably from 30 to 150 parts by weight, more preferably from 50 to 120 parts by weight, per 100 parts by weight of the epoxy resin (A).

When the curing agent (B) is a phenolic curing agent, an amine curing agent or an acid anhydride curing agent, the equivalent ratio of the functional group in the curing agent (B) to the epoxy group in the epoxy resin (A) Preferably, it is used in the range of 0.8 to 1.5, and more preferably in the range of 0.8 to 1.2. If it is outside this range, the functional group of the unreacted epoxy group or the hardener remains, and the desired physical property cannot be obtained.

Further, the curing agent (B) is a guanamine-based curing agent, a tertiary amine, an imidazole or a derivative thereof, an organic phosphine, a phosphonium salt, a tetraphenylboron salt, an organic dioxane, a boron halide amine complex, In the case of a polythiol-based curing agent, an isocyanate-based curing agent, a blocked isocyanate-based curing agent, etc., it is preferably 0.1 to 20 with respect to 100 parts by weight of the epoxy resin (A). It is used in the range of parts by weight, and more preferably in the range of 0.5 to 10 parts by weight.

Further, in the case of the dicyandiamide compound, it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the epoxy resin (A).

[Filler (C)]

The filler (C) is added for the purpose of improving the thermal conductivity and controlling the linear expansion coefficient, and in particular, the main purpose is to control the linear expansion coefficient.

The filler (C) is, for example, at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of the carbon include carbon black, carbon fiber, graphite, fullerene, diamond, and the like. Examples of the metal carbide include tantalum carbide, titanium carbide, tungsten carbide, and the like. Examples of the metal oxide include magnesium oxide, aluminum oxide, cerium oxide, calcium oxide, zinc oxide, cerium oxide, zirconium oxide, cerium oxide, cerium oxide, lanthanum aluminum oxynitride (antimony, aluminum, oxygen, nitrogen). The ceramics formed) and the like. Examples of the metal nitride include boron nitride, aluminum nitride, and tantalum nitride.

The shape of the filler (C) is not limited, and may be a pellet, a whisker, a fiber, a plate, or the like.

In the interlayer filler composition for a laminated semiconductor device, since insulation is required, the filler (C) is preferably an oxide or a nitride. More specific examples of such a filler (C) include alumina (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), tantalum nitride (Si ₃ N ₄ ), and cerium oxide ( SiO ₂ ) and the like. Wherein, preferably Al ₂ O _3, AlN, BN, or SiO _2, particularly preferably Al ₂ O _3, BN or SiO _2.

As the BN-based filler, it is preferred to use Japanese Patent Laid-Open No. 2013-241321 The reporter revealed.

These fillers (C) may be used singly or in combination of two or more kinds in any combination and in any ratio.

In recent years, in order to further improve the performance of high-speed, high-capacity, and the like, the distance between the wafers is reduced to about 10 to 50 μm, but in the interlayer filling layer between the wafers, the filler is prepared. The maximum particle diameter is preferably about 1/3 or less of the thickness of the interlayer filling layer.

When the maximum particle diameter of the filler (C) exceeds 10 μm, the filler (C) protrudes from the surface of the interlayer filling layer after curing, and the surface shape of the interlayer filling layer tends to deteriorate. The maximum particle diameter of the filler (C) is preferably 5 μm, more preferably 3 μm.

The content of the filler (C) of the interlayer filler composition of the present invention is preferably 10 to 500 parts by weight, more preferably 20 parts by weight per 100 parts by weight of the epoxy resin (A) and the hardener (B). ~400 parts by weight. The content of the filler (C) is based on the total of the epoxy resin (A) and the hardener (B) per 100 parts by weight, and if it is less than 10 parts by weight, the addition effect of the filler (C) is small, and the target is not obtained. In the case of a coefficient of linear expansion or thermal conductivity, if it exceeds 500 parts by weight, the presence of the filler (C) may hinder the bondability.

[flux (D)]

The flux (D) specifically includes a metal oxide signal terminal such as a solder bump and a surface oxide film of a land, or a solder bump on the surface of the pad, during soldering of the metal terminal. A compound that wets diffusivity and thus prevents reoxidation of the metal terminal surface of the solder bump.

Examples of the flux (D) used in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, and milk. An aliphatic carboxylic acid such as acid, acetic acid, propionic acid, butyric acid, oleic acid or stearic acid; benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic anhydride, trimesic acid, benzene An aromatic carboxylic acid such as tetracarboxylic acid or an acid anhydride thereof; an organic carboxylic acid such as a terpene carboxylic acid such as rosin acid or rosin; and an organic carboxylic acid of a hemiacetal ester obtained by reacting an organic carboxylic acid with an alkyl vinyl ether. Acid ester; glutamine hydrochloride, aniline hydrochloride, guanidine hydrochloride, cetylpyridinium bromide, phenylhydrazine hydrochloride, tetrachloronaphthalene, methylguanidine hydrochloride, methylamine hydrochloride, ethylamine hydrochloride, Organic halogen compounds such as diethylamine hydrochloride and butylamine hydrochloride; amines such as urea and diethylenetriamine; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, etc. Polyols; inorganic acids such as hydrochloric acid, hydrofluoric acid, phosphoric acid, hydrofluoroboric acid; fluorides such as potassium fluoride, sodium fluoride, ammonium fluoride, copper fluoride, nickel fluoride, and zinc fluoride; potassium chloride and chlorine Sodium chloride, cuprous chloride, nickel chloride, ammonium chloride, zinc chloride, stannous chloride, etc.; potassium bromide, sodium bromide, ammonium bromide, tin bromide, zinc bromide Bromide and so on. These compounds may be used as they are, or may be microencapsulated by using a coating agent such as an organic polymer or an inorganic compound. These compounds may be used alone or in combination of two or more kinds in any combination and in any ratio.

The content of the flux (D) in the interlayer filler composition of the present invention is preferably 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on the total of the epoxy resin (A) and the hardener (B). It is 0.5 to 5 parts by weight. When the content of the flux (D) is less than 0.1 part by weight per 100 parts by weight of the total of the epoxy resin (A) and the curing agent (B), there is a problem that the solder joint is poor due to a decrease in the oxide film removal property. Further, when it exceeds 10 parts by weight, the viscosity of the composition rises and the connection failure occurs.

[hardening accelerator (E)]

The interlayer filler composition of the present invention is used to lower the hardening temperature and shorten the hardening. The hardening accelerator (E) may also be contained together with the hardener (B).

As an example of the hardening accelerator (E), a compound containing a tertiary amino group, imidazole or a derivative thereof, an organic phosphine, dimethyl urea, or a coating agent using an organic polymer or an inorganic compound, or the like is used to apply the above compound. Microencapsulators, etc.

As the compound having a tertiary amino group, 1,8-diazabicyclo(5,4,0)undecene-7, tri-ethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine can be exemplified. Ethanol, ginseng (dimethylaminomethyl) phenol, and the like.

As the imidazole or a derivative thereof, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methyl can be exemplified Imidazole, 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-all three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, an epoxy resin and an adduct of the above imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like.

The organic phosphines may, for example, be tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine or phenylphosphine. The onium salt may, for example, be tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium, ethyltriphenylborate or tetrabutylphosphonium tetrabutylborate. As the tetraphenylboron salt, 2-ethyl-4-methylimidazole‧tetraphenylborate and N-methyl can be exemplified Porphyrin ‧ tetraphenyl borate and the like.

Among these, imidization is preferred from the characteristics of a long pot life, a high hardenability in a medium temperature region, and a high heat resistance of a hardened resin. The compound (imidazole or a derivative thereof) and the application thereof are microencapsulated by using a coating agent such as an organic polymer or an inorganic compound.

These hardening accelerators (E) may be used singly or in combination of two or more kinds in any combination and in any ratio.

In the case where the interlayer filler composition of the present invention contains the hardening accelerator (E), the content of the hardening accelerator (E) is per 100 parts by weight of the total of the epoxy resin (A) and the hardener (B). It is preferably 0.001 to 15 parts by weight, more preferably 0.01 to 10 parts by weight. When the content of the hardening accelerator (E) is less than 0.001 part by weight per 100 parts by weight of the total of the epoxy resin (A) and the curing agent (B), the curing promoting effect is insufficient; if more than 15 parts by weight There is a catalyst hardening reaction that is dominant, and there is no possibility of achieving a reduction in voids.

[Dispersant (F)]

The interlayer filler composition of the present invention preferably contains a dispersing agent (F) in order to improve the dispersibility of the filler (C). The dispersing agent (F) is not particularly limited, and any one known as a dispersing agent formulated in the interlayer filler composition can be used.

In the interlayer filler composition of the present invention, the content of the dispersing agent (F) may be any ratio, and the dispersing agent (F) may be used in an amount of 100 parts by weight of the filler (C). It is preferably 0.1 to 4 parts by weight, more preferably 0.1 to 2 parts by weight.

[Other additives]

In the interlayer filler composition of the present invention, for the purpose of further enhancing the function, various additives other than the above may be contained within a range not impairing the effects of the present invention.

As an example of the additive, for example, a chimeric agent for improving the bondability or the bondability between the epoxy resin (A) and the filler (C), and ultraviolet rays for improving the storage stability can be mentioned. Agents, antioxidants, plasticizers, flame retardants, colorants, fluidity improvers, adhesion promoters to substrates (eg, thermoplastic oligomers).

These other additives may be used singly or in combination of two or more kinds in any combination and in any ratio.

The blending amount of the other additives is not particularly limited, and is used in accordance with the usual amount of the resin composition to the extent that the necessary functionality is obtained; the blending amount of the other additive components is based on the epoxy resin (A) and the hardener ( The total of B) is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less per 100 parts by weight.

The coupling agent may, for example, be a decane coupling agent or a titanate coupling agent.

Examples of the decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and β-(3,4-epoxycyclohexyl)B. Epoxy decane such as trimethoxy decane, γ-aminopropyl triethoxy decane, N-β (aminoethyl) γ-aminopropyl trimethoxy decane, N-β (amino group) Ethyl) γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, etc. Aminodecane, 3-mercaptopropyltrimethyl Tertyl decane such as oxydecane, p-styryl trimethoxy decane, vinyl trichloro decane, vinyl ginseng (β-methoxyethoxy) decane, vinyl trimethoxy decane, vinyl triethoxy A vinyl decane such as a decane or a γ-methacryloxypropyltrimethoxy decane may be used, for example, an epoxy group, an amine group or a vinyl polymer type decane.

Examples of the titanate coupling agent include isopropyl triisostearate isopropyl titanate, isopropyl tris(N-aminoethyl ‧ aminoethyl) titanate, and bis(dioctyl phosphate). Diisopropyl titanate, bis(dioctylphosphonate) tetraisopropyl titanate, tetraoctylbis(di(tridecyl)phosphate) titanate, tetrakis(2,2-diallyl) Oxymethyl-1-butyl) bis(di(tridecane) Base)) titanate phosphate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)extended ethyl titanate, and the like.

These coupling agents may be used singly or in combination of two or more kinds in any combination and in any ratio.

When the interlayer filler composition of the present invention contains a coupling agent, the content thereof is preferably about 0.1 to 2.0% by weight based on the total solid content in the interlayer filler composition. If the amount of the coupling agent is small, the effect of improving the adhesion between the epoxy resin (A) and the filler (C) which are caused by the coupling of the coupling agent cannot be sufficiently obtained; if too much, all the results are obtained. The problem of the hardened material oozing out of the coupling agent.

The interlayer filler composition of the present invention may contain thermoplastic oligomers for the purpose of improving the fluidity during molding and improving the adhesion to the substrate. Examples of the thermoplastic oligomers include a C5-based or C9-based petroleum resin, a styrene resin, a ruthenium resin, a ruthenium styrene copolymer resin, a ruthenium styrene phenol composite resin, and a ruthenium ketone. A polymer resin, a ruthenium benzothiophene copolymer resin, or the like. These may be used alone or in combination of two or more.

In the case where the interlayer filler composition of the present invention contains such thermoplastic oligomers, the content thereof is usually 2 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the epoxy resin (A). .

The interlayer filler composition of the present invention may further contain a surfactant, an emulsifier, a low-elasticity agent, a diluent, an antifoaming agent, an ion scavenger, and the like.

As the surfactant, any of a conventional anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used.

For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkyl benzene sulfonic acids Salts, alkylnaphthalenesulfonates, alkyl sulfates, alkyl sulfonates, sulfonate succinates, alkyl betaines, amino acids, and the like.

Among these surfactants, it is preferred to use a fluorosurfactant in which a part or all of the C-H bond is a C-F bond.

In the case where the interlayer filler composition of the present invention contains such a surfactant, the content thereof is 0.001 to 0.1 part by weight, preferably 0.001 to 0.1 part by weight, based on 100 parts by weight of the total of the epoxy resin (A) and the curing agent (B). 0.003~0.05 parts by weight.

Further, an organic solvent may be further added to the interlayer filler composition of the present invention.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; esters such as ethyl acetate; and ethylene glycol. An ether such as monomethyl ether, an amine such as N,N-dimethylformamide or N,N-dimethylacetamide, an alcohol such as methanol or ethanol, hexane or cyclohexane. An alkane, an aromatic such as toluene or xylene.

In particular, in view of the solubility of the resin and the boiling point of the organic solvent, ketones, esters or ethers such as methyl ethyl ketone or cyclohexanone are preferred, and methyl ethyl ketone and ring are particularly preferred. Ketones such as ketone.

These organic solvents may be used singly or in combination of two or more kinds in any combination and in any ratio.

Among them, when an organic solvent is used, since the organic solvent volatilizes in the bonding step and voids are easily formed in the cured adhesive layer, the interlayer filler composition of the present invention preferably does not contain an organic solvent.

[Method of Manufacturing Interlayer Filler Composition]

The interlayer filler composition of the present invention is usually an epoxy resin (A), a hardener (B), a filler (C), and a flux (D), a hardening accelerator (E) and a dispersing agent (optionally used) ( F) and other additive components are uniformly mixed by a mixer or the like, and then kneaded by a heating roll, a kneader or the like to be produced. The order in which these ingredients are formulated is not particularly limited. Further, it is also possible to form a film by a press or the like after kneading. Further, the pulverization of the melt kneaded material may be further carried out after the kneading to carry out pulverization or granulation.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to the preferred embodiments, but the present invention is not limited to the following examples.

[mixing ingredients]

In the following examples and comparative examples, the formulation components used for the preparation of the interlayer filler composition are as follows.

<Epoxy Resin (A)>

Epoxy resin (A1): manufactured by Daiso Chemical Co., Ltd. under the product name "LX-01" (bisphenol A type epoxy propyl ether epoxy resin, epoxy equivalent 181 g / equivalent, viscosity at 25 ° C 10 Pa‧ s)

Epoxy resin (A2): manufactured by Mitsubishi Chemical Corporation, product name "jER 1032H60" (paraben (hydroxyphenyl) methane type solid epoxy resin, epoxy equivalent 169g / equivalent, melting point 56 ~ 62 ° C)

<hardener (B)>

Amine hardener (B1): manufactured by Wakayama Seika Chemical Co., Ltd., product name "SEIKACURE S" (amine price 124g / equivalent, melting point 177 ° C)

Amine-based hardener (B2): manufactured by IHARA CHEMICAL CORPORATION, under the product name "ELASMER-250P" (polytetramethyleneoxybis-4-aminobenzoic acid ester, amine price 235 g/eq, melting point 60 ° C, The viscosity at 25 ° C is 10 Pa ‧ s)

An acid anhydride hardener (B3): manufactured by Mitsubishi Chemical Corporation under the trade name "jER CURE YH306" (3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1, 2-dicarboxylic anhydride, anhydride equivalent 117 g / equivalent, viscosity at 25 ° C is 0.1 Pa ‧ s)

<Filler (C)>

Inorganic filler (C1): manufactured by Longsen Co., Ltd., product name "MUF-2BV" (melted cerium oxide)

Inorganic filler (C2): manufactured by Longsen Company, the product name "TS-AP-9"

Inorganic filler (C3): Made by Admatechs, under the name "AE9104-SXE"

<flux (D)>

Flux (D1): manufactured by Nippon Oil Co., Ltd., under the name "Santasiddo I" (monoalkyl vinyl ether block difunctional carboxylic acid)

Flux (D2): manufactured by Wako Pure Chemical Co., Ltd., under the name "Pimelic Acid"

<hardening accelerator (E)>

Hardening accelerator (E): Asahi Kasei E-Materials Co., Ltd., product name "NOVACURE HXA3792" (a mixture of microencapsulated amine-based hardener and bisphenol A-type liquid epoxy resin)

<dispersant (F)>

Dispersant (F): "BYK-2155" (block copolymer with pigment affinity group) manufactured by BYK-Chemie Japan Co., Ltd.

[Evaluation of various physical properties and characteristics] (1) Viscosity of interlayer filler composition

The viscosity of the interlayer filler composition (complex viscosity of the dynamic viscoelasticity measurement) was measured using a viscoelasticity measuring apparatus (Physica MCR102) manufactured by Anton Paar Japan Co., Ltd. as follows.

First, the interlayer filler composition belonging to the measurement object is placed on a parallel plate (Parallel Plate Dish) and a parallel plate ( Dynamic viscoelasticity measurements were made between 20 mm).

The measurement conditions were such that the sample was subjected to a sine wave strain of 0.5%, the strain frequency was set to 1 (Hz), and the temperature was raised at a ratio of 3 ° C for 1 minute, and the viscosity during the temperature rise was measured from 40 ° C to 200 ° C. The viscosity at 130 ° C is taken as η ₁₃₀ .

(2) Evaluation of jointability

The resistance of the Daisy Chain inside the manufactured semiconductor element was measured by a four-terminal method by a digital multimeter. The resistance value R1=70 Ω with respect to the outer periphery of the peripheral portion, and the resistance value R2=27 Ω of the inner circumference were evaluated as “○” when the value was ±5%, and “×” when the value exceeded ±5%.

(3) Evaluation of voids in the joint surface

For the semiconductor element to be manufactured, an ultrasonic probe imaging device (FS300III) manufactured by Hitachi Power Solutions Co., Ltd. was used to observe whether or not there was a gap between the bump and the bump between the bonded wafers. The case where the gap is 10 or less is evaluated as "○", and the gap is 11 More than one is evaluated as "X".

[Examples 1 to 18, Comparative Examples 1 to 8]

In a 150 cc stirred vessel, 8.31 g of an epoxy resin (A1), 2.26 g of an amine hardener (B1), and 1.43 g of an amine hardener (B2) were weighed and added in an amount of 1 for the addition of the filler (C). The dispersing agent (F) in a weight part (0.18 g) was stirred at 2000 rpm and 1 kPa for 2 minutes using a self-rotating mixer (ARV-310, manufactured by THINKY Co., Ltd.). Next, 18.0 g of the inorganic filler (C1) was added, and the mixture was stirred at 2000 rpm and 1 kPa for 3 minutes using a self-rotating mixer, and then stirred at 1600 rpm and 1 kPa for 5 minutes. Next, 0.5 part by weight (0.06 g) of the flux (D1) was added to the total amount of the resin, and the mixture was stirred at 1600 rpm and 1 kPa for 5 minutes to prepare an interlayer filler composition. The η ₁₃₀ of the interlayer filler composition is 1 Pa ‧ or less.

The interlayer filler composition was applied to an interposer (IP80 Model I, 10 mm square) manufactured by WALTS Co., Ltd., and heated to 70 ° C while applying about 10 mg (about 20 mg/cm ² per effective area).

The interposer (IP80ModelI) coated with the interlayer filler composition was placed on the platform side, and the solder bump crystal (CC80 Model I, 7.3 mm square) was placed on the indenter side, and hot pressing was performed using Toray Engineering Co., Ltd. The adhesive bonding apparatus "Flip Chip Bonder (FC3000S)" was subjected to heat-pressure bonding at a bonding time shown in Table 1 at 20 N (3.8 Kgf/cm ² ) according to the temperature conditions of the indenter and the stage shown in Table 1. Thereafter, the film was heat-hardened at 165 ° C for 2 hours to produce a semiconductor element.

[Examples 19, 20]

In a 150 cc stirred vessel, weighed 3.56 g of epoxy resin (A1), 3.56 g of epoxy resin (A2), and 4.87 g of an acid anhydride hardener (B3), and the amount of addition was 1 weight relative to the filler (C). The dispersing agent (F) (0.18 g) was stirred at 2000 rpm and 1 kPa for 2 minutes using a self-rotating mixer (ARV-310, manufactured by THINKY Co., Ltd.). Next, 18.0 g of the inorganic filler (C1) was added, and the mixture was stirred at 2000 rpm and 1 kPa for 3 minutes using a self-rotating mixer, and then stirred at 1600 rpm and 1 kPa for 5 minutes. Next, 1.8 g of the hardening accelerator (E) was added, and 0.5 part by weight (0.06 g) of the flux (D1) was added to the total amount of the resin, and the mixture was stirred at 1600 rpm and 1 kPa for 5 minutes to prepare an interlayer filler composition. The η ₁₃₀ of the interlayer filler composition is 1 Pa ‧ or less.

In the same manner as in Example 1, the interlayer filler composition prepared was subjected to heat and pressure bonding in accordance with the bonding conditions shown in Table 1, to produce a semiconductor device.

The semiconductor elements obtained in Examples 1 to 20 and Comparative Examples 1 to 8 were evaluated for adhesion and voids, and the results are shown in Table 1. In Table 1, "Over" means that the pass is poor (resistance value is 1 MΩ or more).

[Examples 21 to 24, Comparative Examples 9 to 10]

In a 150 cc stirred vessel, 1.78 g of epoxy resin (A1), 1.78 g of epoxy resin (A2), and 2.85 g of an acid anhydride hardener (B3) were weighed and added in an amount of 1 part by weight based on the total filler (0.34). The dispersing agent (F) of g) was stirred at 2000 rpm and 1 kPa for 5 minutes using a self-rotating mixer (manufactured by THINKY Co., Ltd., ARV-310). Then, 16.8 g of the inorganic filler (C2) was added, and the mixture was stirred at 1800 rpm and 1 kPa for 5 minutes using a revolving mixer, and then 16.8 g of an inorganic filler (C3) was further added thereto, and the mixture was stirred at 1800 rpm and 1 kPa for 5 minutes. Next, 0.96 g of a hardening accelerator (E) was added, and the mixture was stirred at 1800 rpm and 1 kPa for 5 minutes, and then 1 part by weight (0.06 g) of the flux (D2) was added to the total amount of the resin, and the mixture was stirred at 1800 rpm and 1 kPa for 5 minutes. Interlayer filler composition. The η ₁₃₀ of the interlayer filler composition is 1 Pa ‧ or less.

The interlayer filler composition was applied to an interposer (IP80 Model I, 10 mm square) manufactured by WALTS Co., Ltd., and heated to 70 ° C while applying about 10 mg (about 20 mg/cm ² per effective area).

This was coated with an interposer (IP80ModelI) of interlayer filler composition and a solder bump crystal (CC80ModelI, 7.3 mm square), using a thermocompression bonding device "Flip Chip Bonder (FC3000S) manufactured by Toray Engineering Co., Ltd.). On the side shown in Table 2, an interposer is provided, and according to the temperature conditions of the indenter and the platform shown in Table 2, the pressure is 20 N (3.8 Kgf/cm ² ), and the heating and pressing time is 5 seconds. . Thereafter, the film was heat-hardened at 180 ° C for 2 hours to produce a semiconductor element.

The semiconductor elements obtained in Examples 21 to 24 and Comparative Examples 9 to 10 were evaluated for adhesion and voids, and the results are shown in Table 2.

[Example 25]

The interlayer filler composition used in Example 1 was applied to an interposer (IP80 Model I, 10 mm square) manufactured by WALTS Co., Ltd., and heated to 70 ° C while applying about 2 mg (about 4 mg/cm ² per effective area).

This was coated with an interposer (IP80ModelI) of an interlayer filler composition and a TSV wafer (CC80TSV-2, 7.3 mm square), using a thermocompression bonding device "Flip Chip Bonder (FC3000S) manufactured by Toray Engineering Co., Ltd.). The pressure-bonding was carried out by an indenter temperature of 250 ° C, a table temperature of 250 ° C, a bonding time of 5 sec, and a bonding pressure of 20 N (3.8 Kgf / cm ² ).

Thereafter, the interlayer filler composition was applied to the bonded substrate, and about 8 mg (about 16 mg/cm ² per effective area) was applied while heating to 70° C., and a solder bump wafer (CC80ModelI, 7.3mm square), heated and bonded according to the same conditions. Thereafter, the film was heat-hardened at 165 ° C for 2 hours to produce a semiconductor element.

The junction has no voids and can be confirmed to be conductive. The appearance and cross-sectional photograph of the obtained semiconductor element are shown in Fig. 3 .

[investigation]

It can be seen from Table 1 and Example 25 that the temperature regions surrounded by the above four equations are used under the conditions of the indenter and the platform temperature specified in the present invention, whereby the voids can be reduced, and good jointability and conductivity can be obtained. .

(industrial availability)

According to the method for producing a semiconductor device of the present invention, it is possible to reduce voids in the cured adhesive layer, and it is possible to obtain good bonding properties and conductivity, and to realize a high-quality semiconductor device excellent in reliability.

The contents of the specification, the claims, the drawings and the abstract of the Japanese Patent Application No. 2014-209100, filed on Oct. 10, 2014, and the Japanese Patent Application No. 2015-170906, filed on Aug. 31, 2015, are hereby incorporated by reference. Thus, the disclosure of the present invention is disclosed.

1‧‧‧ solder bumps

1A‧‧‧pad terminal

1B‧‧‧ solder

2‧‧‧Semiconductor wafer

3‧‧‧Interlayer filler composition

4‧‧‧ Coating nozzle

5‧‧‧Interlayer filler composition layer

6‧‧‧electrode pads

7‧‧‧Semiconductor substrate

8‧‧‧ hardened adhesive layer

10‧‧‧Semiconductor components

Claims (14)

A method of manufacturing a semiconductor device, wherein a semiconductor wafer having a solder bump and a semiconductor substrate having an electrode pad are thermally bonded by a thermocompression bonding device via an interlayer filler composition to fabricate a semiconductor device; The temperature of the indenter and the platform of the thermocompression bonding apparatus is set in a graph in which the temperature of the indenter is the vertical axis and the temperature of the platform is the horizontal axis, and the temperature conditions in the range surrounded by the following four equations are performed. Joining; H+1.9S=590...Formula 1 H+0.526S=310...Formula 2 H+0.8S=580...Formula 3 H+1.25S=725...Formula 4 (in the above formulas 1-4, H represents the joint The head temperature (°C), S indicates the platform temperature (°C) at the time of joining). A method of manufacturing a semiconductor device, comprising: a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad, via a thermocompression bonding device having an indenter and a platform capable of individually adjusting temperature, via an interlayer filler composition The thermocompression bonding is performed to manufacture a semiconductor component; the temperature of the indenter and the platform of the thermocompression bonding device is in a graph in which the indenter temperature is the vertical axis and the platform temperature is the horizontal axis. The temperature conditions in the range surrounded by the four equations are joined; H+1.9S=590...Formula 1 H+0.526S=310...Formula 2 H+0.8S=580...Formula 3 H+1.25S=725... 4 (In the formulas 1 to 4, H represents the head temperature (°C) at the time of joining, and S represents the stage temperature (°C) at the time of joining). The method for producing a semiconductor device according to claim 1 or 2, wherein the interlayer filler composition has a viscosity at 130 ° C of 100 Pa ‧ or less. The method of manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the interlayer filler composition contains an epoxy resin (A), a hardener (B), a filler (C), and a flux (D) . The method of producing a semiconductor device according to claim 4, wherein the interlayer filler composition further contains a curing accelerator (E). The method of producing a semiconductor device according to claim 4 or 5, wherein the interlayer filler composition further contains a dispersant (F). The method for producing a semiconductor device according to any one of claims 4 to 6, wherein the curing agent (B) is 30 to 150 parts by weight per 100 parts by weight of the epoxy resin (A). The method for producing a semiconductor device according to any one of claims 4 to 7, wherein the curing agent (B) contains at least one curing agent selected from the group consisting of an amine curing agent and an acid anhydride curing agent. The method for producing a semiconductor device according to claim 8, wherein the hardener (B) is 0.8 to 1.5 in terms of an equivalent ratio of the functional group in the hardener (B) to the epoxy group in the epoxy resin (A). The scope. A method for manufacturing a semiconductor device, comprising: a step of bonding a semiconductor wafer having solder bumps and a semiconductor substrate having an electrode pad via an interlayer filler composition using a thermocompression bonding apparatus; and the thermocompression bonding apparatus The temperature of any of the indenter or the platform is 120 ° C or higher, the solder bump is brought into contact with the electrode pad, and after the solder bump is in contact with the electrode pad, the indenter or the platform is applied to the solder bump and the electrode. The temperature at the side less than 120 ° C at the time of pad contact becomes more than the melting point of the solder. The method of manufacturing a semiconductor device according to claim 10, wherein the interlayer filler is applied in advance to a semiconductor wafer or a semiconductor substrate provided on a side of the indenter or the substrate which is not more than 120 ° C when the solder bump is in contact with the electrode pad. The composition is joined after the composition. The method of producing a semiconductor device according to claim 10 or 11, wherein the interlayer filler composition has a viscosity at 100 ° C of 0.1 to 10 Pa ‧ . The method of producing a semiconductor device according to claim 11 or 12, wherein the interlayer filler composition contains an epoxy resin (A), a hardener (B), a filler (C), and a flux (D). The method of producing a semiconductor device according to claim 13, wherein the interlayer filler composition contains a hardening accelerator (E).