TWI534169B - Die bonding agent - Google Patents

Description

Grain bond

The present invention relates to a die bonding agent, a semiconductor device using the die bonding agent, and a method of manufacturing a semiconductor device.

In the manufacture of a semiconductor device, a die bonding agent is commonly used in a subsequent step of a semiconductor element such as an IC or an LSI and a substrate or a lead frame. Typically, in the next step, the die bond 2 is applied to the substrate 1 and heated to B-stage (semi-harden) the die bond, the semiconductor component 3 is mounted, and then heated and hardened until C stage (final hardening). Thereafter, the electrode portion of the semiconductor element and the circuit pattern of the substrate are connected by a wire 4 (wire bonding), and sealed with a sealant 5 to obtain a semiconductor device 6 (see FIG. 1). An epoxy resin system is proposed for the die bonding agent used in this method (for example, refer to Patent Document 1).

It is understood that the circuit pattern of the electrode portion of the semiconductor element and the substrate is connected by wire (wire), and the grain bonding agent used in the subsequent step of the semiconductor element and the substrate or the lead frame is also insulated. A conductive adhesive containing a thermosetting compound such as an epoxy resin and a conductive filler may be used as the opposite of the insulating adhesive. Conductive adhesive for suppressing migration of conductive filler (ion transfer of conductive filler) In general, there is also a case where there is no B-stage (semi-hardening) and hardening until C-stage (final hardening).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-168906

As described above, in the method of manufacturing a semiconductor device, after the semiconductor element is mounted, the die bonding agent is heated by heating to be hardened until C-stage, and then wire bonding and sealing are performed. It is assumed that even in the case of using a conductive adhesive containing a conductive filler, wire bonding and sealing are performed after hardening until C-stage. In order to improve the productivity and energy efficiency of a semiconductor device, the inventors of the present invention tried to use a die bond and perform wire bonding and sealing without C-stage, but used conventional epoxy resins. In the case of a die bond, it is known that the die bond is melted during wire bonding and sealing, and a problem arises in that the semiconductor element on the die bond used for wire bonding is deviated from the substrate.

An object of the present invention is to provide a die bonding agent which can solve the above problems and which can provide a semiconductor device with excellent reliability by a simple method. Specifically, the subject is to provide a die bonding agent which can be wire-bonded and sealed in a B-stage state even if C-stage is not performed, and a semiconductor device having high reliability can be manufactured.

The present inventors conducted various investigations and found that it is possible to use a specific The hardener solves the problem.

1. The present invention relates to a die bonding agent comprising (A) a solid epoxy resin, (B1) dicyandiamide, and (B2) a carboxylic acid dioxane having a melting point of 170 ° C or less, wherein The ratio of the molar number of the active hydrogen contained in B1) to the number of moles of the epoxy group contained in (A) is 0.9 to 1.8, and the molar number of active hydrogen contained in (B2) is relative to (A) The molar ratio of the epoxy groups contained is 0.08 to 0.35.

2. The present invention relates to a grain bonding agent, wherein (B2) is selected from the group consisting of 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin and 7,11-octadecene One or more kinds of dicarboxylic acid diterpenes in a group of diene-1,18-dicarbene.

The present invention relates to the die bonding agent according to the invention 1 or 2, wherein (A) is a solid bisphenol A type epoxy resin.

The present invention relates to the die bonding agent according to any one of claims 1 to 3, wherein the molar amount of the active hydrogen contained in (B1) is relative to the epoxy group contained in (A). The ratio of the number of ears is 0.9 to 1.4, and the ratio of the molar number of the active hydrogen contained in (B2) to the number of moles of the epoxy group contained in (A) is 0.08 to 0.3.

The present invention relates to the die bonding agent according to any one of claims 1 to 4, which further comprises a glycol ester solvent.

The die bonding agent according to any one of claims 1 to 5, which is obtained by B-staged.

The present invention relates to a semiconductor device produced by using the die bonding agent according to any one of Inventions 1 to 6.

8. The present invention relates to a method of fabricating a semiconductor device, including the following The steps of: (1) applying the die bonding agent according to any one of the inventions 1 to 6 to a substrate; (2) b-stage the grain bonding agent applied to the substrate by heating (3) a step of mounting a semiconductor element on the substrate in a manner adjacent to the B-staged grain bonding agent; and (4) using a sealing agent after bonding the electrode portion of the semiconductor element to the circuit pattern of the substrate The step of sealing.

According to the die bonding agent of the present invention, the semiconductor device can be excellent in reliability in a simple manner. In detail, according to the die bonding agent of the present invention, it is possible to perform wire bonding and sealing in a B-stage state even without C-stage, and it is possible to manufacture a semiconductor device having high reliability.

1‧‧‧Substrate

2‧‧‧Grain bonding agent

3‧‧‧Semiconductor components

4‧‧‧ wire

5‧‧‧Sealant

6‧‧‧Semiconductor device

11‧‧‧Substrate

12‧‧‧Grain bonding agent

13‧‧‧Semiconductor components

14‧‧‧Wire

15‧‧‧Sealant

16‧‧‧Semiconductor device

Fig. 1 is a schematic view showing a conventional method of manufacturing a semiconductor device.

Fig. 2 is a schematic view showing a method of manufacturing a semiconductor device of the present invention.

Fig. 3(a) shows the results of the grain adhesion test of Example 2.

Fig. 3(b) is the result of the grain adhesion test of Comparative Example 6.

The grain bonding agent of the present invention contains (A) a solid epoxy resin. In the present specification, the solid epoxy resin refers to an epoxy resin having a solid shape at room temperature (25 ° C). Since a solid epoxy resin is used, a grain bonding agent is applied to a substrate or the like, and the state of B-stage by heating is non-stick at room temperature. (tack-free), this step is advantageous in terms of preservation and so on.

In the case of (A), a solid o-cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a modified phenol type epoxy resin, a naphthalene type epoxy resin, and a dicyclopentadiene type may be exemplified. Epoxy resin, epoxy propyl amine epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, biphenyl aralkyl epoxy resin, bisphenol F epoxy resin, hydrogenation double A phenol A type epoxy resin, an aliphatic type epoxy resin, a stilbene type epoxy resin, a bisphenol A novolak type epoxy resin, or the like. Among them, from the viewpoint of non-adhesiveness and adhesion at room temperature, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are preferable. (A) Those having a weight average molecular weight of 850 to 2,900, preferably 900 to 1,700 can be used. The solid bisphenol A type epoxy resin may, for example, be a weight average molecular weight of from 900 to 1,700. The weight average molecular weight is a value determined by gel permeation chromatography (GPC) using polystyrene as a standard.

(A) may be used alone or in combination of two or more.

In the crystal grain bonding agent of the present invention, (B1) dicyandiamide and (B2) bismuth carboxylic acid having a melting point of 170 ° C or less are used in combination as a curing agent. (B2) The temperature at which the hardener acts as a starting point is low, and its function is mainly as a hardener in the B-stage of the grain bonding agent. On the other hand, (B1) has a high temperature as a function of the start of the hardener, and its function is mainly as a hardener in the case of the main hardening. By combining (B1) and (B2) having such characteristics, it is possible to exert a sufficient and stable adhesive force in the B-staged state, and to avoid a shift between the substrate and the semiconductor element during wire bonding and sealing.

In the present specification, the carboxylic acid dioxime refers to a compound having two groups represented by the following formula: -C(=O)NHNH ₂ .

From the viewpoint of the adhesion in the B-staged state, the die bond of the present invention uses divalent carboxylic acid having a melting point of 170 ° C or less as (B2). The melting point of (B2) is preferably from 100 to 170 ° C, more preferably from 120 to 160 ° C.

In the case of (B2), 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (melting point: 120 ° C), 7,11-octadecadiene-1, 18-two calories (melting point 160 ° C) and the like. From the viewpoint of preservation stability of the grain bonding agent, 7,11-octadecadiene-1,18-dikacaridine is preferred.

(B2) may be used alone or in combination of two or more.

From the viewpoint of high temperature adhesion strength after the B stage, the grain bonding agent of the present invention can make the number of moles of active hydrogen contained in (B2) relative to the number of moles of epoxy groups contained in (A) The ratio (the number of moles of active hydrogen contained in (B2) / the number of moles of epoxy groups contained in (A)) is 0.08 to 0.35, and (B2) is used, preferably 0.08 to 0.30, more preferably It is 0.10 to 0.30, more preferably 0.12 to 0.28, and particularly preferably 0.15 to 0.25. In the present specification, the number of moles of the active hydrogen contained in (B2) is four times that of the molar number (B2).

From the viewpoint of the bonding strength after the C stage, the grain bonding agent of the present invention is such that the molar number of the active hydrogen contained in (B1) is relative to the number of moles of the epoxy group contained in (A). (B1), preferably 0.9 to 1.5, more preferably, the molar amount of the active hydrogen contained in (B1)/the number of moles of the epoxy group contained in (A) is from 0.9 to 1.8. From 0.9 to 1.4, the best is from 1.0 to 1.4. In the present specification, the molar number of the active hydrogen contained in (B1) is four times that of the molar number (B1). If the ratio of the molar number of the active hydrogen contained in (B1) to the number of moles of the epoxy group contained in (A) is less than the above range, the B-stage state is poor in adhesion. The hygroscopicity is also poor, the reliability is low, and the preservation stability is poor. Moreover, when it is more than the above range, the spreadability is small, good adhesion is not ensured, moisture absorption is also poor, reliability is low, and storage stability is poor.

The grain bonding agent of the present invention can contain a liquid epoxy resin in a range that does not impair the effects of the present invention. In the present specification, the liquid epoxy resin means an epoxy resin which exhibits fluidity at room temperature (25 ° C). The liquid epoxy resin may, for example, be a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, an aminophenol type epoxy resin, or a hydrogenated bisphenol A type epoxy resin. , aliphatic epoxy resin, oxime modified epoxy resin, polyalkylene ether modified epoxy resin, epoxy resin with special soft skeleton, alicyclic epoxy resin, etc. The epoxy resin (for example, bisphenol A type epoxy resin) which is the same as that of the solid epoxy resin can be regarded as being in a state at 25 ° C (that is, it is solid at 25 ° C under normal pressure or liquid) State) and differentiated use. For example, as the solid epoxy resin, a softening point of 50 to 100 ° C can be used. The liquid epoxy resin is preferably 45 parts by mass or less, more preferably 38 parts by mass or less, based on 100 parts by mass of (A).

The grain bonding agent of the present invention can use a resin other than an epoxy resin (hereinafter also referred to as "other resin") within a range that does not impair the effects of the present invention. The other resin may be a thermosetting resin or a thermoplastic resin, and is preferably a solid shape at room temperature (25 ° C). Other resins may, for example, be a phenoxy resin, an acrylic resin, a maleimide resin, a silicon resin, a quinone imine resin, a polyester resin, or a styrene copolymer. Wait. The other resin is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of (A).

The die bond of the present invention can use a hardener of an epoxy resin other than (B1) and (B2) within a range not impairing the effects of the present invention. Examples of such a curing agent include phenol resins, aromatic amines, imidazoles, and carboxylic acids.

The grain bonding agent of the present invention contains an elastomer (acrylonitrile-butadiene rubber, argon oxide elastomer powder, etc.) for the purpose of adjusting the modulus of elasticity, etc.; for the purpose of adjusting the modulus of elasticity, the expansion ratio, the thermal conductivity, and the like. In addition, a filler (silica, alumina, or the like) is contained; a coupling agent (such as a decane coupling agent) is contained for the purpose of adjusting adhesion, and the like, and a rocking agent is contained for the purpose of adjusting the suitability at the time of coating. Additives such as foaming agents, colorants, and leveling agents. The grain bonding agent of the present invention may contain conductive particles.

The grain bonding agent of the present invention may contain a solvent from the viewpoint of coating workability. The solvent is preferably a solvent having high solubility in (A) and low solubility in (B1) and (B2). When (B1) and (B2) are dissolved in a solvent, the hardening of the B-stage is excessive, and the adhesion at the time of mounting and wire bonding of the semiconductor element may cause a problem. The solvent may, for example, be a glycol ester solvent, and examples thereof include ceramide acetate (for example, ethylene glycol monoethyl ether acetate) and carbitol acetate (for example, ethyl carbene). Alcohol acetate, butyl carbitol acetate, etc.); from the viewpoint of handling properties, etc., preferably carbitol acetate, more preferably ethyl carbitol acetate, butyl carbene Alcohol acetate. The amount of the solvent can be appropriately adjusted from the viewpoint of workability, and it is preferably 40% by mass or less in the use of the grain bonding agent.

The grain bonding agent of the present invention can be produced by mixing (A), (B1) and (B2) with any additives and solvents. For example, (A) may be dissolved in a solvent by heating a stirrer or the like, and (B1), (B2), and any addition may be added at room temperature. The mixture is added to the solute of (A), and kneaded by a kneader, a three-pass roll or the like to produce.

The grain bonding agent of the invention can make the viscosity after manufacture to be 20 to 80 Pa at room temperature (25 ° C). s. From the viewpoint of workability, the viscosity is preferably 30 to 70 Pa. s. In the present specification, the viscosity is measured at 25 ° C using an E-type viscometer at a number of revolutions of 5 rpm and a rotor (3° X 9.7 R). The grain bonding agent of the present invention is excellent in storage stability.

The die bonding agent of the present invention can satisfactorily wire and seal the substrate and the semiconductor element, and has good spreadability of the die bond applied to the B-staged state of the substrate, and exhibits sufficient and stable adhesion, and is B-staged. The state of the grain bonding agent is also low in hygroscopicity, and can provide a semiconductor device with high reliability. Further, in the B-staged state, the crystal grain bonding agent of the present invention is non-tacky at room temperature, and is advantageous in terms of storage in a B-staged state, and the storage stability is good.

The semiconductor device 16 can be manufactured by using the die bonding agent of the present invention, and can include a manufacturing method of the following steps.

(1) a step of applying the die bond 12 of the present invention to the substrate 11; (2) a step of B-staged the die bond applied to the substrate by heating; (3) abutting a step of B-staged grain bonding agent, a step of mounting the semiconductor element 13 on the substrate; and (4) a step of sealing the circuit pattern of the semiconductor element and the circuit pattern of the substrate, and sealing using the sealing agent 15 in the step (4) In the case where the sealant is heat-hardened and sealed, B The grain bonding agent in the stage state is completely hardened (refer to Fig. 2).

By using the die bonding agent of the present invention, wire bonding and sealing can be performed even after the semiconductor device is mounted and hardened by heating until the C-stage is completed as in the conventional semiconductor device method. However, the die bonding agent of the present invention can also be used in a conventional method in which a semiconductor element is mounted and then cured by heating until C-stage. It can also be used in a method of manufacturing a semiconductor device which is not subjected to wire bonding or sealing.

The coating method of the die bonding agent is not particularly limited, and drawing/printing can be performed using a dispenser, a screen, or the like.

The heating temperature at the time of B-staged the grain bonding agent applied to the substrate is preferably 100 to 150 °C. As long as it is in this temperature range, it is possible to exhibit sufficient adhesion in the B-stage state. The heating temperature at the time of B-stage is more preferably 120 to 150 °C.

The mounting method of the semiconductor element is not particularly limited and can be performed by a mounter or the like. The semiconductor component can be mounted as needed, for example, at 60 to 150 ° C, for example, a load of 10 to 100 N/chip.

The method of bonding the electrode portion of the semiconductor element and the circuit pattern of the substrate is not particularly limited, and may be performed by a wire bonder or the like.

After the wire is applied, in order to protect the member, a sealant may be used for sealing, but the method at this time is not particularly limited. As the sealant, a molding varnish which is well known in the art can be used, and examples thereof include an epoxy molding compound (EMC; Epoxy Molding Compound). The molding resin can usually be hardened by heating at 160 to 180 °C. When the grain bonding agent of the present invention has a B-stage state before sealing, it can be hardened by heating at this time, and the substrate and the semiconductor element are connected. More sturdy.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples.

(Examples 1 to 7, Comparative Examples 1 to 6)

The composition shown in Table 1 (the numerical values in the table are parts by mass), and the components were mixed to prepare a crystal grain bonding agent of the example/comparative example. The characteristics of each grain bonding agent were measured in the following manner.

[Save stability]

The grain bonding agent of the example/comparative example was measured using an E-type viscometer (product name TV-20, manufactured by Toki Sangyo Co., Ltd.) at 25 ° C, a number of revolutions of 5 rpm, and a rotor (3 ° X 9.7 R). Post-viscosity (initial viscosity) and viscosity after a predetermined period of storage in a closed container (post-adhesion).

Calculate [{(post-time viscosity)-(initial viscosity)}/(initial viscosity)]×100 (%)

When it is less than 1 week and increases by 20% or more, it is ×

○ when it is less than 2 weeks and increases by 20% or more

When it is increased by more than 20% for more than 3 weeks, it is ◎

[sticky]

Using a printing machine (plate thickness: 50 μm), the die bonding agent of the example/comparative example was applied to a stainless steel substrate (40 mm × 60 mm) in a size of 30 mm × 50 mm, and then heated at 140 ° C for 60 minutes to carry out B-stage. Thereafter, the viscosity was measured at room temperature using a Tack Tester (manufactured by RHESCA, product name: TAC-II). It is preferably less than 10 gf.

Condition: down speed 1.0mm/sec pull-up speed 600mm/sec load 100gf time 1 second measurement distance 5mm probe diameter 5mmφ

[adhesiveness (die attach)]

The film was bonded in the same manner as the viscosity test (however, it was applied to a size of 5 mm × 5 mm), and a film of the grain-bonding agent of the Example/Comparative Example which was B-staged was prepared, and an adapter (manufactured by Panasonic Factory Solutions Co., Ltd.) was used. , product name FCB3), the wafer which has been heated at 140 ° C is mounted at a load of 2 kg / 5 mm ² for 0.5 seconds. Observation was carried out using an ultrasonic test equipment (product name: HiSpeed 1000TM, manufactured by Insight Co., Ltd.), and the wafer was ○ when it was mounted without voids, and was × when voids were generated.

The third (a) and third (b) drawings correspond to the second embodiment and the comparative example 6, respectively.

[Continuity (high temperature adhesion)]

The tantalum wafer was attached to the film of the grain-bonding agent of the B-staged Example/Comparative Example in the same manner as the adhesion (die adhesion). Thereafter, the substrate was heated at 180 ° C, and the bonding strength between the substrate and the tantalum wafer was measured using a tabletop strength tester (manufactured by DAGE Co., Ltd., product name Universal Bonder Series 4000).

[Adhesiveness (subsequent hardening followed by strength)]

The tantalum wafer was attached to the film of the grain-bonding agent of the B-staged Example/Comparative Example in the same manner as the adhesion (die adhesion). After that, It was heated at 175 ° C for 60 minutes for formal hardening. The adhesion strength between the substrate and the tantalum wafer was measured at room temperature using a tabletop strength tester (manufactured by DAGE Co., Ltd., product name Universal Bonder Series 4000).

[Expandability]

On the BGA substrate, the line-and-space (hereinafter referred to as L/S) of the grain bonding agent of the example/comparative example was 2.8 mm/1.4 mm, and the line pitch was 9.7 mm. The stencil printing was carried out in a manner of /2 mm, and B-staged by heating at 140 ° C for 60 minutes. On the B-staged grain bonding agent, a wafer having a thickness of 330 μm, a length of 5 mm, and a width of 5 mm which had been heated at 140 ° C was mounted at a load of 2 kg/5 mm ² for 0.5 second. The spreadability of the die bond developed from the edge of the wafer (the length from the edge of the wafer to the spread of the die bond) was measured. Further, the evaluation of the developability was ○ when the developed length of the die bond from the edge of the wafer was 50 to 250 μm, and was × when it exceeded 250 μm.

[Moisture Reflux Test]

Using a printing machine (plate thickness: 50 μm), the grain bonding agent of the example/comparative example was applied to a BGA substrate (40 mm × 60 mm) so as to have a size of 30 mm × 50 mm, and then heated at 140 ° C for 60 minutes to carry out B. Staged. In the film of the grain bonding agent of the example/comparative example of the B-stage, a bonder (product name FCB3, manufactured by Panasonic Factory Solutions Co., Ltd.) was used, and the thickness was 330 μm and the length was 3 mm, which was heated at 140 ° C. The wafer having a width of 3 mm was mounted at a load of 2 kg/5 mm ² for 0.5 second, and 10 test pieces each of the die bonding agents of the examples and the comparative examples were produced. Each test piece was observed using an ultrasonic detecting device (SAT: manufactured by Insight Co., Ltd., product name HiSpeed 1000TM), and it was confirmed that the substrate and the wafer were not peeled off. Then, each test piece was placed in boiling water and boiled for 2 hours. Each test piece was taken out from boiling water and placed on a hot plate at 270 ° C for 30 seconds. Thereafter, each test piece was observed using the same ultrasonic detecting device as described above. It was confirmed that all of the ten test pieces were ○ when the substrate and the wafer were not peeled off, and it was confirmed that at least one of the ten test pieces was × when the substrate was peeled off from the wafer.

Solid epoxy resin

Ep1: bisphenol A type epoxy resin epoxy equivalent 475g/eq softening point 64 ° C Mw about 900

EP2: bisphenol A epoxy resin Epoxy equivalent 650g / eq Softening point 78 ° C Mw about 1200

Ep3: bisphenol A type epoxy resin epoxy equivalent 925g/eq softening point 97 ° C Mw about 1650

Ep4: an aralkyl type epoxy resin containing a biphenyl skeleton (NC3000 manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 276 g/eq, softening point 56 ° C Mw about 960

Liquid epoxy resin

Ep5: bisphenol A epoxy resin Epoxy equivalent 189g/eq

Carboxylic acid

DH1: 7,11-octadecadiene-1,18-dikane (melting point 160 ° C)

DH2: 3-bis(decylcarboxyethyl)-5-isopropylhydantoin (melting point 120 ° C)

DH3: Dioxadiamine (melting point 180 ° C)

DH4: Dioxonium dodecanoate (melting point 190 ° C)

Phenolic novolac resin (H-4 manufactured by Minghe Chemical Co., Ltd.)

As shown in Table 1, the grain bonding agents of Examples 1 to 7 corresponding to the grain bonding agents of the present invention are non-viscous at room temperature after the B-stage, and are advantageous in terms of storage and the like. Further, in the B-staged state, good spreadability and good adhesion are exhibited, and the germanium wafer can be mounted without voids. Furthermore, in the B-stage state, the adhesion is excellent, and the high temperature is excellent in strength, even if it is sucked again. No peeling occurred in the wet reflow test, and the adhesion after the main hardening was also good, and it was confirmed that a semiconductor device excellent in reliability can be provided. Among them, Examples 2 to 7 using 7,11-octadecadiene-1,18-dicarbene were excellent in storage stability.

The grain bonding agent of Comparative Example 1 which lacked bismuth carboxylic acid had a high temperature bonding strength.

The grain bonding agents of Comparative Examples 2 and 3 using a bismuth carboxylic acid having a high melting point also had poor high-temperature bonding strength. Further, the die bonding agent of Comparative Example 3 has a large spreadability, and the reliability required for miniaturization and densification is low.

The grain bonding agent of Comparative Example 4 using a phenol novolak resin as a curing agent had a high temperature bonding strength and a difference in strength after the main curing, and the storage stability was also low. Further, the die bonding agent of Comparative Example 4 had a large spreadability and was peeled off by the moisture absorption reflow test, and the reliability was low.

Further, Comparative Example 5 in which the content of bismuth carboxylate was lower than the range of the present invention and Comparative Example 6 which was higher than the range of the present invention was inferior in terms of adhesion. Specifically, in Comparative Example 5, the high-temperature adhesion strength was poor, and peeling occurred due to the moisture absorption reflow test, and the reliability was low. In Comparative Example 6, voids were generated when the tantalum wafer was mounted, and the strength at the high temperature was also poor, and the spreadability was small, and peeling occurred due to the moisture absorption reflow test, and the reliability was low.

(Examples 8 to 12, Comparative Examples 7 to 10)

The composition shown in Table 2 (the numerical values in the table are parts by mass), and the components were mixed to prepare a crystal grain bonding agent of the examples/comparative examples. The solid epoxy resin, the liquid epoxy resin, and the carboxylic acid diterpene were used in the same manner as those shown in Table 1. The characteristics of each grain bonding agent were measured in the same manner as described above.

As shown in Table 2, the grain bonding agent of Examples 8 to 12 corresponding to the grain bonding agent of the present invention using 7,11-octadecadiene-1,18-dikalan was used after the B-stage. It is non-viscous at room temperature and is beneficial in terms of preservation. Moreover, in the B-staged state, good adhesion is exhibited, and the germanium wafer can be mounted without voids. Further, in the B-staged state, the adhesion is excellent, and the high-temperature bonding strength is excellent. In addition, the adhesion after the final hardening is also good, and the storage stability is also excellent. Further, it was confirmed that the grain bonding agents of Examples 8 to 12 have good developability, and no peeling occurred after the moisture absorption reflow test, and a semiconductor device excellent in reliability can be provided.

The expansion ratio of the molar number of the active hydrogen contained in (B1) dicyandiamide to the molar number of the epoxy group contained in (A) is lower than that of Comparative Example 7 in the range of the present invention. It is large, peeling occurs due to moisture absorption reflow test, low reliability, poor storage stability, and poor strength after formal hardening.

The expansion ratio of the molar number of the active hydrogen contained in (B1) dicyandiamide to the molar number of the epoxy group contained in (A) is higher than that of Comparative Example 8 in the range of the present invention. It is small in nature and peels off due to moisture absorption and reflow, and has low reliability and poor storage stability.

Further, the ratio of the molar number of the active hydrogen contained in the (B2) bismuth carboxylic acid to the molar number of the epoxy group contained in (A) is Comparative Example 9 which is lower than the range of the present invention. In other words, the high temperature is inferior in strength, and peeling occurs due to the moisture absorption reflow test, and the reliability is low, and the storage stability is poor.

The ratio of the molar number of the active hydrogen contained in (B2) bismuth carboxylic acid to the molar number of the epoxy group contained in (A) is higher than that of Comparative Example 10 in the range of the present invention. Low spreadability, peeling due to moisture absorption reflow test, reliable Low degree and poor preservation stability.

(industrial availability)

According to the die bonding agent of the present invention, the semiconductor device can be excellent in reliability in a simple manner. In detail, even if it is not C-staged, it is possible to perform wire bonding and sealing in a B-stage state, and it is possible to manufacture a semiconductor device having high reliability, and it is industrially highly usable.

The first item of the patent application scope of the present application is a grain bonding agent. However, the drawing of the present invention is a schematic diagram of a manufacturing method of a semiconductor device or a photograph of an experimental result, and thus is not sufficient to represent the technical features of the present invention.

Claims (7)

A grain bonding agent comprising (A) a solid epoxy resin, (B1) dicyandiamide, and (B2) a carboxylic acid dihydrazide having a melting point of 170 ° C or less, wherein (B1) contains active hydrogen The ratio of the number of ears to the number of moles of the epoxy group contained in (A) is 0.9 to 1.4, and the number of moles of active hydrogen contained in (B2) is relative to the number of epoxy groups contained in (A). The ratio of the number of ears is 0.08 to 0.30. The grain bonding agent according to claim 1, wherein (B2) is selected from the group consisting of 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin and 7,11- One or more carboxylic acid diterpenes in a group of octadecadiene-1,18-dikason. The grain bonding agent according to claim 1 or 2, wherein (A) is a solid bisphenol A type epoxy resin. The grain bonding agent according to claim 1 or 2, which further comprises a glycol ester solvent. The grain bonding agent according to claim 1 or 2, wherein the grain bonding agent is B-staged. A semiconductor device manufactured by using the die bonding agent according to any one of claims 1 to 5. A method of manufacturing a semiconductor device, comprising the steps of: (1) applying a die bond according to any one of claims 1 to 5 to a substrate; (2) heating by a step of B-staged the grain bonding agent applied to the substrate; (3) in a manner of adjoining the B-staged grain bonding agent a step of mounting a semiconductor element on a board; and (4) a step of sealing the circuit pattern of the electrode portion of the semiconductor element and the substrate, and then sealing with a sealant.