JP2009209191A - Liquid resin composition for underfill, semiconductor device using the same, and method for producing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid resin composition excellent in heat-resistant adhesiveness. <P>SOLUTION: Provided are the liquid resin composition for underfills, characterized by comprising (A) an epoxy resin represented by formula (1), (B) a cyanate ester compound, (C) acrylonitrile-butadiene copolymer containing a vinyl group at a terminal, and (D) a filler; and a semiconductor device produced with the liquid resin composition for the underfills. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid resin composition for underfill, a semiconductor device using the same, and a method for manufacturing a semiconductor device.

The flip chip mounting method was developed in response to the demand for higher integration and higher density of semiconductor chips and miniaturization of semiconductor packages. The mounting method is not connected by wire bonding so far, but the semiconductor chip surface and the printed wiring board are connected by solder bumps, thereby enabling a reduction in size and thickness. However, since the thermal expansion coefficients of the semiconductor chip, the printed wiring board, and the solder are different, thermal stress is generated during the thermal shock test. In particular, thermal stress is concentrated locally on the solder bump near the corner far from the center of the semiconductor chip. For this reason, cracks occur in the solder bumps, and the operation reliability of the circuit is greatly reduced. Therefore, sealing with a liquid injection sealing underfill material is performed for the purpose of reducing thermal stress. Specifically, a liquid injection sealing underfill material is injected into a gap (30 to 150 μm) between the semiconductor chip and the printed wiring board, cured, and sealed. (For example, refer to Patent Document 1.)
In order to relieve and absorb the above-mentioned thermal stress on the solder bump, the liquid injection sealing underfill material has physicochemical characteristics.
(1) Matching the thermal expansion coefficient (α1) below the glass transition temperature of the liquid injection sealing underfill material with the thermal expansion coefficient of the solder bump.
(2) The glass transition temperature (Tg) of the liquid injection sealing underfill material is high. That is, the temperature range of the thermal expansion coefficient (α1) below the glass transition temperature is wide.
(3) Adhesion at the interface between the liquid injection sealing underfill material-semiconductor chip or the liquid injection sealing underfill material-printed wiring board.
Etc. are required. In the liquid injection sealing underfill material satisfying these requirements, the sealing resin filled in the gap with respect to the external temperature change expands and contracts similarly to the solder, and each interface is firmly bonded. Thermal stress is distributed throughout the semiconductor package, and connection reliability is maintained. In addition, the liquid injection sealing underfill material also serves to protect the circuit surface of the semiconductor chip and the solder bumps from the external environment. As described above, the reliability of flip chip mounting largely depends on the liquid injection sealing underfill material. With the rapid spread of flip chip mounting in recent years, a more reliable liquid injection sealing underfill material is desired. (Specifically, moisture absorption treatment is performed under conditions such as JEDEC levels 3 and 4, and IR reflow test and temperature cycle test are performed).

JP 2006-233351 A

However, many of the liquid resin compositions for underfill used for liquid injection sealing underfill materials that are currently in practical use are significantly less reliable when subjected to moisture absorption treatment, or as the glass transition temperature is increased. Thus, the liquid resin composition has a drawback that its filling property is remarkably lowered. Furthermore, in order to satisfy the moisture resistance reliability, the adhesion of (4) (3) above should not be changed as much as possible by the moisture absorption treatment as the characteristics other than the above (1) to (3).
(5) The injectability and fillability as a liquid resin composition for underfill are ensured. Is important.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a more reliable liquid resin composition for underfill.
Another object of the present invention is a cured product having excellent flow characteristics such as injectability and filling properties as a liquid resin composition for underfill, and does not impair adhesion to a semiconductor chip by moisture absorption treatment, and has a high glass transition temperature. Is to provide a liquid resin composition excellent in heat-resistant adhesion.

Such an object is achieved by the present inventions [1] to [6] below.
[1] (A) an epoxy resin represented by formula (1), (B) a cyanate ester compound, (C) a copolymer containing at least one vinyl group at a terminal, and (D) a filler. A liquid resin composition for underfill characterized by the above.

[2] The underfill for [1] above, wherein the copolymer containing a vinyl group at at least one of the terminals (C) is a copolymer of acrylonitrile, butadiene and acrylic acid. Liquid resin composition.
[3] The liquid resin composition for underfill according to [1] or [2], wherein the cyanate ester compound (B) is represented by the following formula (2).

（Ｒ１〜Ｒ６は、それぞれ独立して水素原子、メチル基、ＣＦ₃基、ハロゲン原子のいず
れかを表わす。）

(R1 to R6 each independently represent a hydrogen atom, a methyl group, a CF ₃ group, or a halogen atom.)

[4] The underfill liquid resin composition according to any one of [1] to [3], further including (E) a bisphenol compound represented by the following formula (3):

（Ｒ１〜Ｒ６は、それぞれ独立して水素原子、メチル基、ＣＦ₃基、ハロゲン原子のいず
れかを表わす。）

(R1 to R6 each independently represent a hydrogen atom, a methyl group, a CF ₃ group, or a halogen atom.)

[5] A semiconductor device comprising a circuit board, a semiconductor chip disposed on the circuit board, and an underfill filling the gap between the two,
A semiconductor device, wherein the underfill is obtained by curing the underfill liquid resin composition according to any one of [1] to [4].
[6] A method for manufacturing a semiconductor device comprising a circuit board, a semiconductor chip disposed on the circuit board, and an underfill filling the two gaps,
Filling the gap between the circuit board and the semiconductor chip with the underfill liquid resin composition according to any one of [1] to [4],
Curing the filled underfill liquid resin composition to underfill;
A method for manufacturing a semiconductor device, comprising:

  An object of the present invention is to provide a highly reliable liquid resin composition for underfill by using the above liquid resin composition, which is excellent in fluidity characteristics such as injectability and fillability, and can be used for a semiconductor chip by moisture absorption treatment. An object of the present invention is to provide a liquid resin composition that gives a cured product having a high glass transition temperature and is excellent in heat-resistant adhesion without impairing the adhesion.

The present invention comprises (A) an epoxy resin represented by formula (1), (B) a cyanate ester compound, (C) a copolymer containing at least one vinyl group at the terminal, and (D) a filler. The present invention relates to an underfill liquid resin composition.
In addition, the following is an illustration and this invention is not limited to these at all.
Hereinafter, each component of the liquid resin composition for underfill of the present invention will be described in detail.

The epoxy resin used in the liquid resin composition for underfill of the present invention is (2- [4- of the epoxy resin (A) represented by the formula (1) in order to express high heat resistance and moisture absorption adhesion. (
2,3-epoxypropoxy) -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane]).
Further, if necessary, a novolac type epoxy resin such as a phenol novolac type epoxy resin or a cresol novolac type epoxy resin, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, N, N-diglycidylaniline, Aromatic glycidylamine type epoxy resins such as N, N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin , Triphenolpropane-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified epoxy resin Aralkyl type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, You may use it, mixing suitably with alicyclic epoxy resins, such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipade.
In this case, those in which a glycidyl structure is bonded to an aromatic ring are preferable from the viewpoints of heat resistance, mechanical properties, and moisture resistance. In particular, polyglycidyl ether obtained by reaction of bisphenol A, bisphenol F, phenol novolak and epichlorohydrin is 25 ° C. In addition, it is preferable to use a liquid-like material because the workability and pot life of the resin composition are excellent. In addition, those having a glycidylamine structure bonded have a reduced pot life, and an alicyclic epoxy resin has a reduced reliability, particularly an adhesive property. Therefore, it is preferable to limit the amount used. Further, from the viewpoint of ensuring the reliability of the semiconductor device, it is preferable that the epoxy resin to be used has as little ionic impurities as Na ⁺ and Cl ⁻ .
(A) The compounding quantity of the epoxy resin represented by Formula (1) and epoxy resins other than Formula (1) is 20-300 weight with respect to 100 weight part of epoxy resins represented by (A) Formula (1). Part is preferable, and 30 to 200 parts by weight is more preferable. By setting it as this range, it will be excellent in heat resistance, mechanical characteristics, and moisture resistance. Moreover, it is preferable that the resin composition of this invention is finally liquid at normal temperature (25 degreeC) as an epoxy resin, and an epoxy resin solid at normal temperature melt | dissolves in a liquid epoxy resin at normal temperature, and becomes liquid. If it is, it will not be restrict | limited in particular.

The cyanate ester compound (B) used in the present invention is not particularly limited in molecular weight or structure as long as it contains two or more cyanate ester (—O—C≡N) groups in one molecule. In this case, those containing a structure in which a cyanate ester (—O—C≡N) group is bonded to an aromatic ring are preferable from the viewpoint of heat resistance, mechanical properties, and moisture resistance, and cyanate ester (—O— The structure in which the C≡N) group is bonded is preferably limited in terms of reliability, particularly adhesiveness. A molecular structure represented by the formula (2) includes a structure in which a cyanate ester (—O—C≡N) group is bonded to an aromatic ring.
Specific examples include 4,4′-ethylidene diphenyl dicyanate, 4,4′-methylidene bis [2,6-dimethylphenylene cyanate], 4,4 ′-(1-methylethylidene) bis [2-methylphenylene. Cyanate], 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenylene cyanate], 4,4′-methylenebis [2-methylphenylene cyanate], 4,4 ′-(1-methyl-ethylidene) ) Bis [2- (1,1-dimethylethyl) phenylene cyanate] and the like, and these may be used alone or in combination as required. Among these, 4,4′-ethylidene diphenyl dicyanate which exhibits a liquid state at 25 ° C. is preferable from the viewpoint of workability of the resin composition.
Although the compounding quantity of the cyanate ester compound (B) used for this invention does not have a restriction | limiting in particular, Preferably, an epoxy resin is 20-80 weight part with respect to 100 weight part of cyanate ester compounds, More preferably, it is 30-70 weight. Part. By setting it as this range, it is possible to make a resin composition excellent in heat resistance, mechanical properties, and moisture resistance.

The copolymer (C) containing at least one vinyl group at the terminal used in the present invention is used to obtain a liquid resin composition for underfill excellent in injectability and filling properties. Examples of the copolymer (C) include a copolymer of acrylonitrile, butadiene and acrylic acid, and a copolymer containing 1,3-butadiene monomer, acrylonitrile monomer and acrylic acid monomer as repeating units in the molecule. As long as it is a polymer and contains at least one carbon double bond group (C = C) at the end of the molecule, the molecular weight and the bond structure are not particularly limited. The number average molecular weight of the copolymer is preferably in the range of 2,000 to 5,000, and more preferably in the range of 3,000 to 4,000. When the molecular weight is lower than these ranges, the heat resistance is low, and when the molecular weight is high, the viscosity of the liquid resin composition becomes high, causing a problem in workability. The number average molecular weight here is a molecular weight in terms of styrene by GPC method. In this case, the content of acrylonitrile units in the copolymer is preferably 10 to 30 mol%. If it is less than 10 mol%, it is separated because of poor compatibility with the resin component, and if it exceeds 30 mol%, the viscosity of the liquid resin composition is high, causing problems in workability.
The vinyl group introduction site may be at one or both ends of the copolymer of acrylonitrile, butadiene and acrylic acid, or a side chain, and both may be present together. An example of a method for introducing a vinyl group includes a method of adding glycidyl acrylate or glycidyl acrylate after adding a carboxyl group by introducing an acrylic acid monomer to the end of the copolymer. The carbon double bond (C = C) in this case is a carbon double bond (C = C) derived from (meth) acrylate. As an example of the above (C), HYCAR VT polymer VTBNx1300x33 manufactured by Ube Industries, Ltd. can be obtained as a commercial product.
The blending amount of the copolymer containing a vinyl group at at least one of the terminals (C) used in the present invention is 0.5 to 5 parts by weight with respect to 100 parts by weight of the component excluding the filler from the liquid resin composition. More preferably, it is in the range of 2 to 4 parts by weight. Here, when the value is less than the lower limit, the effect of imparting the filling property and the filling property is small, and when the value exceeds the upper limit, the viscosity of the liquid resin composition is remarkably increased.

The filler (D) used in the present invention includes, for example, silicates such as talc, calcined clay, unfired clay, mica, glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), synthetic silica, Oxides such as silica powder such as crystalline silica, carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, barium sulfate, calcium sulfate and calcium sulfite Sulfates or sulfites such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate and other borates, aluminum nitride, boron nitride, silicon nitride and other nitrides it can. These fillers may be used alone or in combination.
Among these, fused silica, crystalline silica, and synthetic silica powder are preferable because the heat resistance, moisture resistance, strength, and the like of the liquid resin composition can be improved.
The shape of the filler is not particularly limited, but the shape is preferably spherical from the viewpoint of viscosity and flow characteristics. In the case of assembling a semiconductor device, the average particle diameter of the filler is preferably 0.1 μm or more and 30 μm or less, and particularly preferably 0.2 μm or more and 8 μm or less. When the average particle diameter is less than the above range, the fluidity of the liquid resin composition is remarkably increased, so that the fluidity is impaired. When the average particle diameter exceeds the above range, the liquid resin composition is clogged with filler when flowing to the semiconductor device. This is not preferable because partial unfilling or poor filling occurs. The filler content relative to 100 parts by weight of the total liquid resin composition is in the range of 30 to 80 parts by weight, more preferably 40 to 70 parts by weight. If the content is less than% in the above range, the thermal expansion coefficient of the liquid resin composition is large, which is not preferable for reducing the reliability of the semiconductor device. Since clogging occurs when flowing in the gap between the chip and the printed wiring board, it is not preferable. Further, the filler may be used alone as long as it is in the above range, or may be mixed so as to have multimodality in the particle size distribution.

In the present invention, (E) one containing a bisphenol compound represented by the following formula (3) can also be used. R1 to R6 in the formula each independently have a structure of a hydrogen atom, a methyl group, a CF ₃ group, an allyl group, or a halogen atom. Specifically, bisphenol A, bisphenol F, bisphenol E, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol E, dicondensates of polycondensates of allylphenol and formaldehyde. Of these, tetramethylbisphenol A and tetramethylbisphenol F, which exhibit good catalytic activity and storage stability, are particularly preferred.
The amount of the (E) bisphenol compound used in the present invention is preferably in the range of 0.5 to 5.0 parts by weight, more preferably 100 parts by weight of the component excluding the filler from the liquid resin composition. Is in the range of 2 to 4 parts by weight. Here, when it is less than the lower limit, the adhesion imparting effect is small, and when it exceeds the upper limit, the flow characteristics of the liquid resin composition deteriorate, which is not preferable.

（Ｒ１〜Ｒ６は、それぞれ独立して水素原子、メチル基、ＣＦ₃基、アリル基、ハロゲン
原子のいずれかを表わす。）

(R1 to R6 each independently represent any of a hydrogen atom, a methyl group, a CF ₃ group, an allyl group, and a halogen atom.)

  In the liquid resin composition for underfill of the present invention, a catalyst for promoting the reaction may be used as necessary. The catalyst is not particularly limited in terms of molecular weight or bond structure as long as it has active hydrogen in the molecule or a metal compound. Examples of the catalyst having active hydrogen include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples of metal compound catalysts include cobalt, zinc, iron, copper, chromium, manganese, nickel, titanium and other metal naphthenates, salts of acetylacetonate, or derivatives thereof, and various carboxyls. There are organometallic complex catalysts such as acid salt alkoxides, and these may be used alone or in combination. In particular, 2-undecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and cobalt acetylacetonate are preferable because they exhibit good storage stability and curing characteristics. The catalyst is contained in an amount of 0.3 to 2 parts by weight with respect to 100 parts by weight of the epoxy resin. Here, if the catalyst is less than 0.3 part by weight with respect to 100 parts by weight of the epoxy resin, the curing time is long, and if it is 2 parts by weight or more, the pot life is short and the workability is lowered.

  In the liquid resin composition for underfill of the present invention, in addition to the above components, other resins, coupling agents such as epoxy silane, diluents, pigments, flame retardants, leveling agents, antifoaming agents, etc. Additives can be used. The liquid resin composition for underfill can be produced by, for example, dispersing and kneading each component, additive and the like with a three-roll, two-heat roll, and vacuum mixer, and defoaming under vacuum.

The most suitable use of the liquid resin composition of the present invention is the flip chip type semiconductor device HYPERLINK.
"http://www8.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=235&N0500=4E#N/;>9<;9=<=///&N0001=187&N0552=9&N0553=000010" \ t "tjitemdrw". A flip chip semiconductor device is a semiconductor chip and a circuit board that are electrically connected via solder bumps. Solder bumps are often made of an alloy consisting of tin, lead, silver, copper, bismuth, etc., and electrical connection methods include flip-chip bonders, etc. After aligning the solder bumps, the solder bumps are heated to a melting point or higher using an IR reflow device, a hot plate, or other heating device, and the metal pads on the circuit board and the solder bumps are formed by fusion bonding. At this time, a solder paste or a solder layer having a relatively low melting point may be formed on the metal pad portion on the circuit board. The electrically connected semiconductor device has a form in which metal bumps exist in a columnar shape in a parallel gap between the semiconductor chip and the circuit board.
The method of using the liquid resin composition of the present invention is such that the liquid resin composition of the present invention is fluidized, injected, and filled into a parallel gap between the semiconductor chip and the circuit board using a capillary phenomenon, a pressure difference, etc., and then cured. A method of sealing by applying a liquid resin composition to a circuit board or a semiconductor chip in advance by printing or needle drawing, bonding the opposing semiconductor chip or circuit board, and heating to a temperature higher than the melting point of the solder bump In addition, there is a method in which electrical connection and curing of the liquid resin composition are performed together, and any method may be used.

Example 1
As the raw material, NC6000 (manufactured by Nippon Kayaku Co., Ltd.) is used as the epoxy resin (A) represented by the formula (1), and EXA-830LVP (Dainippon Ink Chemical Co., Ltd.) is used as an epoxy resin other than the formula (1). Co., Ltd.), L-10 (manufactured by Huntsman Advanced Materials Co., Ltd.) as the cyanate ester compound (B), and VTBNx1300x33 (Ube Industries, Ltd.) as the copolymer (C) containing a vinyl group at the terminal )) As a copolymer of acrylonitrile, butadiene and acrylic acid containing a carboxyl group at the terminal, CTBN1300x1300x31 (manufactured by Ube Industries), and BIS26-X-A (Honshu Chemical Industries (E)) as a bisphenol compound (E) C11ZZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an imidazole catalyst and metal catalyst CoAA (manufactured by Nacalai Tesque Co., Ltd.), KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, MA100R as filler (D), SE6200, SO-E2 (Admatechs Co., Ltd.) as a coupling agent )) Was sufficiently mixed using a planetary mixer and three rolls, followed by vacuum defoaming to prepare a liquid resin composition for underfill. Evaluation was made by the following method.

  The viscosity was measured using a Brookfield viscometer equipped with a CP-51 type cone at 25 ° C. and 5 rpm. The viscosity measurement result of the liquid resin composition obtained in Example 1 was 11 Pa · s. The viscosity of the liquid resin composition is preferably 35 Pa · s or less in consideration of the quantitative supply stability to the semiconductor device, the coating supply property to the semiconductor device, and the flow characteristics to the gap.

As a pot life evaluation method, a liquid resin composition for underfill was prepared, the viscosity after 24 hours at 25 ° C. was measured, the viscosity was measured by the method described above, and the rate of increase in viscosity after 24 hours at 25 ° C. was calculated from the following formula. Calculated.
Viscosity increase rate (%) after 24 hours at 25 ° C. = viscosity after 24 hours at 25 ° C./viscosity before standing for 24 hours at 25 ° C. × 100
The increase in viscosity of the liquid resin composition obtained in Example 1 after 24 hours at 25 ° C. was 11%. Considering the production cycle of the semiconductor device, it is preferably 200% or less.

  The measuring method of glass transition temperature (Tg) is as follows. First, the liquid resin composition obtained in Example 1 was cured at 165 ° C. × 120 minutes, and then a 5 × 5 × 10 mm test piece was obtained by cutting. This test piece was measured using a Seiko TMA / SS120 with a compression load of 5 g and a temperature range of −100 ° C. to 300 ° C. under a temperature increase rate of 10 ° C./min. The glass transition temperature (Tg) was calculated from the intersection of the two tangents of the TMA curve obtained by this TMA type measuring apparatus.

(Fabrication of semiconductor devices)
The liquid resin composition obtained in Example 1 was filled and sealed in the gap between the semiconductor chip and the circuit board connected by solder bumps, and a resin filling test, a mounting reflow test, and a temperature cycle test were performed. The components of the semiconductor device used for testing and evaluation are as follows.
As a semiconductor chip, a PHASE-2TEG wafer manufactured by Hitachi Ultra LSI Co., which has a circuit protective film made of polyimide and a solder bump formed of lead-free solder of Sn / Ag / Cu composition is 15 mm × 15 mm × 0.8 mmt. Cut and used.
The circuit board is based on a 0.8mmt glass epoxy substrate equivalent to FR5 manufactured by Sumitomo Bakelite Co., Ltd., and a solder resist PSR4000 / AUS308 manufactured by Taiyo Ink Mfg Co., Ltd. is formed on both sides, and the solder bump array described above is formed on one side. The one provided with a gold-plated pad corresponding to was cut into a size of 50 mm × 50 mm and used. TSF-6502 (manufactured by Kester, rosin flux) was used as a flux for connection.
To assemble a semiconductor device, first apply a uniform flux of about 50 μm thickness to a sufficiently smooth metal or glass plate using a doctor blade, and then use a flip chip bonder to lightly contact the circuit surface of the semiconductor chip with the flux film. After that, the flux was transferred to the solder bumps, and then the semiconductor chip was pressed onto the circuit board. A heat treatment was performed in an IR reflow furnace, and solder bumps were melted and produced. After melt bonding, cleaning was performed using information using a cleaning liquid. In the filling and sealing method of the liquid resin composition, a semiconductor chip bonded on a circuit board is heated on a hot plate at 110 ° C., and the liquid resin composition prepared on one side of the semiconductor chip is applied and injected and filled. Thereafter, the resin was heated and cured in an oven at 150 ° C. for 120 minutes to obtain a semiconductor device for evaluation test.

  As the resin filling test, the void generation rate was confirmed using an ultrasonic flaw detector after the completion of curing of the produced semiconductor device. In the semiconductor device produced using the liquid resin composition obtained in Example 1, no poor filling voids were observed and good filling properties were shown.

As a test method for the mounting reflow test, the above-mentioned semiconductor device was subjected to a JEDEC level 4 moisture absorption treatment (treatment at 30 ° C. and 60% relative humidity for 92 hours), followed by IR reflow treatment (peak temperature 260 ° C.) three times. The presence or absence of peeling inside the semiconductor device was confirmed using an ultrasonic flaw detector, and the surface of the resin composition on the side surface of the semiconductor chip was further observed using an optical microscope to observe the presence or absence of cracks. In the semiconductor device produced using the liquid resin composition obtained in Example 1, peeling and cracking were not observed, and good reliability was shown.

As the temperature cycle test, the semiconductor device subjected to the above mounting reflow test was subjected to (−55 ° C.
/ 30 minutes) and (125 ° C./30 minutes), and the presence or absence of peeling between the semiconductor chip and the resin composition interface inside the semiconductor device is confirmed with an ultrasonic flaw detector every 250 cycles. Using a microscope, the surface of the resin composition on the side surface of the semiconductor chip was observed to observe the presence or absence of cracks. In the semiconductor device produced using the liquid resin composition obtained in Example 1, peeling and cracking were not observed even after 1000 cycles, and good reliability was shown. Using 10 semiconductor devices, the number of defects after 1000 cycles / 10 was displayed, and the case where all 10 pieces were peeled and cracked before 1000 cycles was marked with x. The above results are summarized in Table 1.

(Example 2)
A liquid resin composition was obtained in the same manner as in Example 1 except that MEH-8000H was used instead of Bis26-X-A. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the evaluation results.

(Example 3)
Instead of using C11Z, a liquid resin composition was obtained in the same manner as in Example 1 except that 2PHZ was used. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the evaluation results.

Example 4
A liquid resin composition was obtained in the same manner as in Example 1 except that HP-4032D was used instead of using EXA-830LVP. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the evaluation results.

(Examples 5 and 6)
A liquid resin composition was obtained in the same manner as in Example 1 except that the amount of NC6000 and the other epoxy resin was changed. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the evaluation results.

(Examples 7 and 8)
A liquid resin composition was obtained in the same manner as in Example 1 except that the amount of VTBN was changed. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the evaluation results.

(Comparative Example 1)
A liquid resin composition was obtained in the same manner as in Example 1 except that L10 was not used. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.
(Comparative Examples 2 and 3)
A liquid resin composition was obtained in the same manner as in Example 1 except that it was changed to EXA-830LVP and HP-4032D without using NC6000. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.
(Comparative Example 4)
A liquid resin composition was obtained in the same manner as in Example 1 except that no filler was used. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.
(Comparative Example 5)
A liquid resin composition was obtained in the same manner as in Example 1 except that VTBN was not used. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.
(Comparative Example 6)
A liquid resin composition was obtained in the same manner as in Example 1 except that VTBN and Bis26-X-A were not used. Using the obtained liquid resin composition, it was evaluated in the same manner as in Example 1, and further, a semiconductor device was prepared and evaluated in the same manner as in Example 1. Table 2 summarizes the evaluation results.

The raw materials in Table 1 will be described below.
EXA-830LVP: Dainippon Ink & Chemicals, Inc., liquid bisphenol F type epoxy resin, epoxy equivalent 161
HP-4032D: manufactured by Dainippon Ink & Chemicals, Inc., 1,6-bis (2,3-epoxypropoxy) naphthalene epoxy equivalent 141
NC6000: manufactured by Nippon Kayaku Co., Ltd., 2- [4- (2,4- (2,3-epoxypropoxy) -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) ) Phenyl) ethyl) phenyl) propane L-10: Huntsman Advanced Materials Co., Ltd., 4,4'-ethylidene diphenyl dicyanate VTBNx1300x33: Ube Industries, Ltd., acrylonitrile containing a vinyl group at the end Copolymer of butadiene and acrylic acid CTBN 1300 × 1300 × 31: manufactured by Ube Industries, Ltd., copolymer of acrylonitrile and butadiene containing a carboxyl group at the end Bis26-XA: manufactured by Honshu Chemical Industry Co., Ltd., tetramethylbisphenol A
MEH-8000H: manufactured by Meiwa Kasei Co., Ltd., polycondensate of allylphenol and formaldehyde (hydroxyl equivalent 141)
C11Z: manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-undecylimidazole 2PHZ: manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-phenyl-4,5-dihydroxymethylimidazole CoAA: manufactured by Nacalai Tesque, Inc., reagent, acetylacetone second Cobalt KBM-403: Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, molecular weight 236.3, theoretical coverage area 330 m ² / g
MA100R: manufactured by Mitsubishi Chemical Corporation, carbon black SE6200: manufactured by Admatechs Co., Ltd., synthetic spherical silica, average particle size 2.5 μm
SO-E2: manufactured by Admatechs Co., Ltd., synthetic spherical silica, average particle size 0.5 μm

  In Table 1, Examples in which (A) an epoxy resin represented by formula (1), (B) a cyanate ester compound, (C) a copolymer containing a vinyl group at the terminal, and (D) a filler are combined. Nos. 1 to 8 show good resin filling characteristics in the evaluation of semiconductor devices, excellent heat resistance adhesion because there is no peeling after 1000 cycles of temperature cycle test, and excellent stress absorption, thermal shock because there is no crack. It was shown to combine with sex.

Next, in the case of the comparative example 1 which does not use (B) cyanate ester compound, since the glass transition temperature of hardened | cured material is low, adhesiveness was very low by the mounting reflow test and the temperature cycle test, and the evaluation test was interrupted.
(A) In the case of Comparative Example 2 that does not contain the epoxy resin represented by formula (1), the viscosity is low and the fluidity is good, but cracks are observed in 750 cycles of the temperature cycle, and cracks are observed in 1000 cycles. The peeling progressed from.
In the case of Comparative Example 3, in the temperature cycle test, the evaluation test was interrupted because peeling occurred.
In the case of Comparative Example 4, cracks were observed in the temperature cycle test in the mounting reflow test and temperature cycle test using the semiconductor device as in Comparative Example 2, and the evaluation test was interrupted.
In the case of Comparative Example 5, unfilled and voids were observed. In the mounting reflow test and the temperature cycle test, the evaluation test was suspended because peeling occurred due to unfilled portions and voids.
In the case of Comparative Example 6, the filling property was good, but in the mounting reflow test and the temperature cycle test, peeling occurred and the evaluation test was interrupted.

  INDUSTRIAL APPLICABILITY The present invention is used in a liquid resin composition having excellent stress absorption, thermal shock resistance, thermal adhesiveness, flow characteristics and sufficient usable time, and a semiconductor device using the liquid resin composition.

Claims (6)

(A) an epoxy resin represented by formula (1),
(B) a cyanate ester compound,
(C) A liquid resin composition for underfill, comprising: a copolymer containing a vinyl group at at least one of terminals; and (D) a filler.

  2. The liquid resin composition for underfill according to claim 1, wherein the copolymer containing a vinyl group at at least one of the terminals (C) is a copolymer of acrylonitrile, butadiene and acrylic acid. . The liquid resin composition for underfill according to claim 1 or 2, wherein the (B) cyanate ester compound is represented by the following formula (2).

(R1 to R6 each independently represent a hydrogen atom, a methyl group, a CF ₃ group, or a halogen atom.) The liquid resin composition for underfill according to any one of claims 1 to 3, further comprising (E) a bisphenol compound represented by the following formula (3).

(R1 to R6 each independently represent a hydrogen atom, a methyl group, a CF ₃ group, or a halogen atom.) A semiconductor device comprising a circuit board, a semiconductor chip disposed on the circuit board, and an underfill filling the gap between the two,
A semiconductor device, wherein the underfill is obtained by curing the underfill liquid resin composition according to any one of claims 1 to 4. A method of manufacturing a semiconductor device comprising a circuit board, a semiconductor chip disposed on the circuit board, and an underfill filling the gap between the two,
Filling the gap between the circuit board and the semiconductor chip with the liquid resin composition for underfill according to any one of claims 1 to 4,
Curing the filled underfill liquid resin composition to underfill;
A method for manufacturing a semiconductor device, comprising: