JP4747580B2 - Liquid sealing resin composition for underfill, semiconductor device using the same, and manufacturing method thereof - Google Patents

Description

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

Conventionally, underfill liquid encapsulating resin composition containing epoxy resin, curing agent and inorganic filler, the surface of the inorganic filler is chemically modified with a silane coupling agent and subjected to acid treatment or basic treatment, and inorganic filling It has been made to improve the dispersibility of the material or improve the adhesion (Patent Documents 1 and 2).
JP2001-024005 JP 2002-226673 A

However, according to the prior art described in the above document, when the flux component is added to the resin composition, the fillers aggregate even if the surface-treated inorganic filler is used, and the linear expansion coefficient and elastic modulus become non-uniform. The problem was left in the point.
The present invention has been made in view of the above circumstances, and an object thereof is to relieve stress in the resin and reduce cracks and warpage.

The present invention for solving the above problems is as follows.
[1] (A) an epoxy resin, (B) a curing agent, (C) a first silane coupling agent, and (D) an inorganic filler in which the second silane coupling agent is chemically modified on the surface layer. a liquid sealing resin composition for underfill by blending, one acidic group of the first silane coupling agent and a second silane coupling agent and the other have a basic group, the acid The group is a thiol group or a functional group that thermally decomposes to generate a thiol group, and the basic group is an amino group or a functional group that thermally decomposes to generate an amino group, and has the basic group The liquid sealing resin composition for underfill , wherein the silane coupling agent is a secondary aminosilane coupling agent .
[2] Further, (E) a third coupling agent is blended, and the (E) third coupling agent includes either an epoxy silane coupling agent or an acrylic silane coupling agent [1]. The liquid sealing resin composition for underfill as described.
[3] The secondary aminosilane coupling agent in which the first silane coupling agent is the silane coupling agent having the acidic group and the second silane coupling agent has the basic group. The liquid sealing resin composition for underfill according to [1] or [2].
[4] The first silane coupling agent is at the secondary amino silane coupling agent having a basic group, and said second coupling agent is a silane coupling that having a said acidic group The liquid sealing resin composition for underfill according to claim 1 , which is an agent .
[5] A liquid sealing resin for underfill according to any one of claims 1 to 4, further comprising a substrate, a chip disposed on the substrate, and an underfill filling the two gaps. A semiconductor device obtained by curing a composition.
[6] A method of manufacturing a semiconductor device comprising a substrate, a chip disposed on the substrate, and an underfill filling the two gaps, wherein (I) the gap between the substrate and the chip is defined in claims 1 to 4. A step of filling the underfill liquid encapsulating resin composition according to any of the above, and (II) curing the filled underfill liquid encapsulating resin composition to form an underfill. Production method.

  ADVANTAGE OF THE INVENTION According to this invention, the stress in resin can be relieve | moderated because an inorganic filler disperse | distributes moderately, and the liquid sealing resin composition for underfills with which the crack and curvature were reduced can be provided.

  The present invention comprises mixing (A) an epoxy resin, (B) a curing agent, (C) a first coupling agent, and (D) an inorganic filler in which the second coupling agent is chemically modified on the surface layer. A liquid sealing resin composition for underfill, wherein one of the first coupling agent and the second coupling agent has an acidic group and the other has a basic group. The present invention relates to a liquid sealing resin composition. The following is an example, and the present invention is not limited to the following. Below, each component of the liquid sealing resin composition for underfills of this invention is demonstrated in detail.

The (A) epoxy resin used in the present invention is not particularly limited in molecular weight and structure as long as it has two or more epoxy groups in one molecule. For example, novolak type phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, phenol resin such as resol type phenol resin, novolak type epoxy resin such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type Aromatic glycidylamine type such as epoxy resin, bisphenol type epoxy resin such as bisphenol F type epoxy resin, N, N-diglycidylaniline, N, N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine Epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, toner Phenolpropane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl having phenylene and / or biphenylene skeleton Type epoxy resin, epoxy resin such as aralkyl type epoxy resin such as naphthol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, alicyclic type such as vinylcyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy-adipide Aliphatic epoxy resins such as epoxy are listed.
In this case, those containing a structure in which a glycidyl ether structure or a glycidylamine structure is bonded to an aromatic ring are preferable from the viewpoint of heat resistance, mechanical properties, and moisture resistance, and aliphatic or alicyclic epoxy resins are particularly reliable and adhesive. In view of the above, it is preferable to limit the amount used. These may be used alone or in combination of two or more. In the present invention, because of the mode of the liquid sealing resin composition for underfill, it is preferable that the epoxy resin is finally liquid at room temperature (25 ° C.). And dissolved in a liquid epoxy resin so long as it is in a liquid state.

  The (B) curing agent used in the present invention includes two or more functional groups capable of forming a covalent bond with an epoxy group in an epoxy resin, provided that the functional group is an acid anhydride group. In some cases, the molecular weight and structure are not particularly limited as long as they contain one or more acid anhydride functional groups. Specific examples of functional groups include phenolic hydroxyl groups, acid anhydrides, primary amines, and secondary amines.

  Examples of curing agents containing two or more phenolic hydroxyl groups include novolak type phenol resins such as phenol novolak resin and cresol novolak resin, triphenolmethane type phenol resin, triphenolpropane type phenol resin, terpene modified phenol resin, dicyclopentadiene Examples thereof include a modified phenol resin such as a modified phenol resin, a phenol aralkyl resin having a phenylene and / or biphenylene skeleton, an aralkyl type phenol resin such as a naphthol aralkyl resin having a phenylene and / or a biphenylene skeleton, and a bisphenol compound.

  Examples of curing agents containing one or more acid anhydride functional groups include tetrahydro anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydro Phthalic anhydride, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydrotri Melitte) monoacetate, dodecenyl succinic anhydride and the like.

  Examples of curing agents containing two or more primary amines or secondary amines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine aliphatic polyamine , Cycloaliphatic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis Piperazine type polyamines such as (2-amino-2-methylpropyl) piperazine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-amino) Nzoeto), polytetramethylene oxide - di -P- aminobenzoate, aromatic polyamines such as those represented by the following formula.

R: hydrogen group or alkyl group X: hydrogen group or alkyl group

The above curing agents may be used alone or in combination with two or more kinds of curing agents containing the same functional group, and as long as the pot life and the curability with the epoxy resin are not impaired. You may mix and use 2 or more types of hardening | curing agents containing a different functional group. Considering the sealing application of the semiconductor device, a phenol resin and an aromatic polyamine type curing agent are preferable from the viewpoint of heat resistance and electromechanical characteristics. Furthermore, an aromatic polyamine type curing agent is preferable from the viewpoint of having both adhesion and moisture resistance. Further, considering that the aspect of the present invention is a liquid sealing resin composition for underfill, those exhibiting a liquid state at room temperature (25 ° C.) are preferable. Specific examples of such aromatic polyamine curing agents include Curing agents disclosed in Kaihei 10-158365 (in formula 1, n = 0 to 2, X = C ₂ H ₅ , R = H), curing agents disclosed in JP-A Nos. 2004-35668 and 133970 (formula 1, n = average 0.3, X = H, R = CH ₃ ) and the like are available.

  The blending amount of the (B) curing agent used in the present invention is in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3 in terms of the active hydrogen equivalent of the curing agent with respect to the epoxy equivalent of the epoxy resin. Here, when the active hydrogen equivalent of the curing agent is less than 0.6 or exceeds 1.4, the reactivity and the heat resistance of the composition are remarkably impaired. However, in the case where the functional group contained in the curing agent is an acid anhydride group, two carboxylic acid functional groups are derived from one acid anhydride functional group, so 2 per acid anhydride functional group. Calculated as including one active hydrogen.

(C) 1st coupling agent used by this invention is a coupling agent mix | blended with a resin composition by an integral blend system or a masterbatch system, As the chemical structure, an alkoxy group couple | bonds in one molecule. It has a chemical structure including a hydrocarbon part in which a metal atom and a functional group are bonded. The metal atom is not particularly limited as long as the bonded alkoxy group reacts with water to produce an alcohol group, but from the viewpoint of filling characteristics of the liquid sealing resin composition for underfill, silicon and aluminum are used. Titanium and zirconia are preferable, and silicon and titanium more preferably provide good adhesion between the resin composition and the semiconductor device.
Here, the integral blend method is an addition method in which a coupling agent is blended, dispersed and mixed at the same time when an inorganic filler and an organic material are mixed in the process of producing a resin composition. In this method, the coupling agent is dispersed and dissolved in advance in (A) an epoxy resin, (B) a curing agent, and / or an organic additive other than the inorganic filler, and then added to the resin composition.

  The acidic group refers to a functional group containing active hydrogen, and specifically includes a thiol group and a functional group that generates a thiol group by thermal decomposition. Specific examples of functional groups that generate a thiol group by thermal decomposition include disulfide and tetrasulfide structures. Specific examples of the coupling agent having an acidic group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxysilylpropyl). Disulfides, and their titanate coupling agents. These may be used alone or in combination of two or more.

  The basic group is a functional group having a nitrogen atom to which one or two active hydrogens are bonded, or a functional group that generates the functional group by reaction thermal decomposition. The former basic group includes an amino group or an N-phenylamino group, and the latter basic group includes a ketimine group obtained by protecting a primary amino group with a ketone or an aldehyde. Specific examples of the coupling agent having a basic group include N-aminoethylated aminopropylmethyl dialkoxysilane, N-aminoethylated aminopropyltrialkoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrialkoxysilane. Ethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminobutyltrimethoxysilane, N-phenyl-γ-aminobutyltriethoxysilane N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) propylamine, N- (benzylidene) -3- (triethoxysilyl) propylamine, and titanate coupling agents thereof. . These may be used alone or in combination of two or more.

  The addition amount of the (C) first coupling agent used in the present invention is 0.03 to 5.0% by weight, more preferably 0.1 to 3.0% by weight, based on the total resin amount. Here, the total resin amount means the total weight of all components excluding the inorganic filler in the resin composition. When the amount of the first coupling agent exceeds 0.03% by weight, the dispersibility of the inorganic filler is improved, and the adhesion of the semiconductor device to the silicon chip is further improved, preferably exceeding 5.0% by weight. If not, it is preferable because bubbles caused by alcohol generated from the coupling agent during resin curing can be suppressed.

  In the present invention, (D) an inorganic filler in which the second coupling agent is chemically modified on the surface layer is used. Here, the second coupling agent is a process of producing a resin composition, and (A) an epoxy resin, (B) a curing agent, and (C) a first coupling agent in the surface layer of the inorganic filler. First, it refers to a coupling agent to be chemically modified, and its chemical structure may be any as long as it has a chemical structure including a metal atom to which an alkoxy group is bonded and a hydrocarbon portion to which a functional group is bonded in one molecule. The metal atom is not particularly limited as long as the bonded alkoxy group is hydrolyzed to form a hydroxyl group, but from the viewpoint of filling characteristics of the liquid sealing resin composition for underfill, silicon, aluminum, titanium Zirconia is preferable, and more preferably, silicon forms a good chemical bond with the surface of the inorganic filler and can improve the mechanical properties of the resin composition.

  Silica powders such as talc, calcined clay, unfired clay, mica, glass and other silicates, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), synthetic silica, crystalline silica, etc. Oxides such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates such as barium sulfate, calcium sulfate, calcium sulfite, or sulfite Examples thereof include salts, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride. These inorganic 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 resin composition can be improved.

  The shape of the inorganic filler is not particularly limited, but the shape is preferably spherical from the viewpoint of filling characteristics. In this case, the average particle size of the inorganic filler is preferably 0.1 to 20 microns, particularly preferably 0.2 to 8 microns. If the average particle size exceeds 0.1 microns, the viscosity of the resin composition decreases, so that the filling property is improved. If the average particle size does not exceed 20 microns, the resin clogging hardly occurs when the composition fills the gaps in the semiconductor device. preferable.

  The chemical modification method is not particularly limited as long as the surface of the inorganic filler can be uniformly treated. Examples of such a method include the following methods. A dry method in which a stock solution of a coupling agent or a solution diluted with toluene, acetone, alcohol, etc. is mixed and stirred while sprayed onto the inorganic filler particles, and after the inorganic filler is immersed and slurried in the coupling agent solution There is a wet method to remove the solvent, a vaporization method in which the coupling agent is vaporized by heating at a reduced pressure or above the boiling point in a sealed container, and the inorganic filler particles are mixed and stirred in the coupling agent vaporization atmosphere. -The third method is more preferable in that uniform chemical modification is possible on the surface of the inorganic filler.

  The state of chemical modification includes (1) when a hydroxyl group present on the surface layer of the inorganic filler and the second coupling agent are (1) dehydrated or dealcoholized to form a condensation reaction to form a covalent bond; (2) hydrogen In the case of chemical adsorption by bonding, (3) three modification states can be taken, ie, physical adsorption, but in any case, there is no problem even if these states are mixed, and the mechanical properties of the resin composition From the viewpoint of strength, it is preferable to include a chemical modification by a covalent bond.

  The amount of the second coupling agent added to the surface of the inorganic filler is 0.03 to 5% by weight, more preferably 0.1 to 1.0% by weight, based on the amount of the inorganic filler. When the amount added is less than 0.1% by weight, the degree of improvement in dispersibility of the inorganic filler in the resin composition is low, and when it is 5% by weight or more, the particles of the inorganic filler are cross-linked and cause particle aggregation.

  Further, within the range in which the dispersibility of the inorganic filler is not impaired, (D) a normal inorganic filler whose surface layer is not chemically modified in addition to the inorganic filler whose second coupling agent is chemically modified on the surface layer May be used in part. In this case, the inorganic filler whose surface layer is not chemically modified is 50% by weight or less, more preferably 25% by weight or less of the total inorganic filler. Content of the inorganic filler in all the resin compositions is 30 to 75 weight%, More preferably, it is 40 to 68 weight%. When the content is less than 30% by weight, the thermal expansion coefficient of the resin composition is large, which is not preferable for reducing the reliability of the semiconductor device. When the content exceeds 75% by weight, the gap is filled in the semiconductor device. Since clogging occurs, it is not preferable.

In the present invention, the acidic group and the basic group of the first coupling agent and the second coupling agent form a chemical bond or chemical interaction such as a hydrogen bond or an acid-base reaction. Is preferred. In such a case, the surface of the inorganic filler is covered with more coupling agent, and the dispersibility in the resin is improved.
In addition to the above case where the first coupling agent is bonded to the inorganic filler via the second coupling agent, the first coupling agent may be directly bonded to the inorganic filler. obtain. Even in this case, the object of improving dispersibility and fluidity of the present invention can be achieved.

  The (E) third coupling agent used in the present invention includes either an epoxy silane coupling agent or an acrylic coupling agent. The epoxy silane coupling agent has a chemical structure including a silicon atom to which an alkoxy group is bonded and a hydrocarbon portion to which an epoxy group is bonded in one molecule. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane. An acrylic silane coupling agent has a chemical structure including a silicon atom to which an alkoxy group is bonded and a hydrocarbon portion to which an acrylate group is bonded in one molecule. Specifically, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. There is.

  (E) The addition amount of the third coupling agent is 0.5 to 5.5% by weight, more preferably 1.5 to 4.5% by weight, based on the total resin amount. Here, the total resin amount means the total weight of all components of the resin composition excluding the inorganic filler. When the added amount of the third coupling agent is less than 0.5% by weight, the adhesion of the semiconductor device to the substrate surface is reduced, and when it exceeds 5.5% by weight, the third cup is cured during resin curing. This is not preferable because bubbles are generated by alcohol generated from the ring agent.

  The liquid sealing resin composition for underfill of the present invention may contain a flexibility imparting material as necessary. In this case, the flexibility-imparting agent is a thermoplastic resin that exhibits a liquid or rubber state at 22 ° C. or higher, and more preferably has a polybutadiene skeleton. These form a sea-island structure in the resin composition and improve the flexibility and fracture toughness of the resin composition. Specific examples include acrylonitrile-polybutadiene rubber, modified products thereof, and epoxy-modified polybutadiene rubber. The resin composition of the present invention may further include a colorant such as carbon black, a flame retardant such as antimony or brominated epoxy resin, a leveling agent, a surfactant such as a wettability improver or an antifoaming agent, if necessary. Other additives may be blended.

  According to the present invention, the inorganic filler is highly dispersed, and a uniform linear expansion coefficient and elastic modulus are realized, so that stress in the resin is delocalized, and cracks, warping stress, and the like are less likely to occur. The liquid sealing resin composition for use can be provided. Moreover, the liquid sealing resin composition for underfill excellent in fluidity | liquidity can be provided. By having excellent fluidity, bubbles are not generated at the time of filling, and the productivity is improved.

  The semiconductor device of the present invention is not particularly limited as long as it uses a flux. Specifically, a flip chip type semiconductor device can be given. A flip chip semiconductor device is a device in which a chip and a substrate are electrically connected via solder bumps. Solder bumps are often made of an alloy consisting of tin, lead, silver, copper, bismuth, etc., and as a method of electrical connection, metal pads on the board and metal bumps on the chip using a flip chip bonder, etc. After the alignment, the metal bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the metal pad and the metal bump on the substrate are formed by fusion bonding. At this time, a solder paste or a metal layer having a relatively low melting point may be formed in advance on the metal pad portion on the substrate. Prior to this electrical joining step, flux is applied to the metal bumps and / or the surface layer of the metal pad portion of the substrate. In addition to this bonding step, flux may be used when forming metal bumps on the chip. Any flux may be used as long as it has a function of removing the oxide film on the metal surface that hinders fusion bonding and improving the melt wettability between metals. The semiconductor device to which electrical connection is made has a form in which metal bumps exist in a columnar shape in a parallel gap between the chip and the substrate, and this gap is filled and sealed with the resin composition of the present invention.

  As a method for producing the resin composition of the present invention, an epoxy resin, a curing agent, a first coupling agent, a third coupling agent, and (D) an inorganic filler in which the second coupling agent is chemically modified on the surface layer Other additives may be blended simultaneously or separately, and dispersed, mixed, kneaded, and cured. More preferably, the first coupling agent and the inorganic filler in which the second coupling agent is chemically modified on the surface layer are dispersed and mixed, and then cured at a temperature of 5 ° C. to 30 ° C. for 12 to 96 hours. It is preferable. The dispersion, mixing, and kneading methods are not particularly limited, and any of a planetary mixer, ball mill, three rolls, two rolls, vacuum mixer, or other kneading apparatus may be used. Or you may use it combining the said apparatus, but in order to remove the bubble contained in the resin composition finally, a vacuum defoaming process is performed.

  As a method for filling and sealing the gap of the semiconductor device of the present invention, it is usual to apply the resin composition to one end of the chip while heating the semiconductor device and the resin composition, and to spread the gap by the capillary phenomenon. Although it is a method, for the purpose of shortening the production cycle, a method of inclining the semiconductor device or accelerating the implantation using a pressure difference may be used in combination. The filled resin is cured by heating in a temperature range of 100 ° C. to 170 ° C. for 1 to 12 hours. Here, for example, the temperature profile may be heat-cured while changing the temperature stepwise, such as heating at 100 ° C. for 1 hour and then heating at 150 ° C. for 2 hours.

Example 1
As epoxy resin (A), 50 parts by weight of bisphenol F type epoxy resin (specific compounds are described in the notes in Table 1. The same applies hereinafter), 50 parts by weight of trifunctional glycidylamine, coupling agent (C) As a mercaptosilane coupling agent (acidic) 0.5 parts by weight, epoxy silane coupling agent 5.7 parts by weight, and treated silica (D) as spherical synthetic silica (basic silane coupling agent-treated product) 306. Add 8 parts by weight of low stress agent 6.5 parts by weight, diluent 2 parts by weight, pigment 0.5 parts by weight using a planetary mixer and 3 rolls, and curing at 25 ° C for 24 hours. As B), 50 parts by weight of aromatic primary amine curing agent is blended, mixed using a planetary mixer and three rolls, and subjected to vacuum defoaming treatment. The use liquid encapsulating resin composition was prepared.

  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 resin composition obtained in Example 1 was 22 Pa · s. The viscosity of the composition is preferably 35 Pa.sec or less in consideration of the stability of quantitative supply to the semiconductor device, the coating supply property to the semiconductor device, and the flow characteristics into the gap.

  For the flow time measurement method, 18 mm x 18 mm upper glass and a slide glass that is sufficiently larger than the upper glass are bonded together using a spacer-containing adhesive so that the gap is 80 um, and a parallel plate is produced. It was put on and preheated, the resin composition was applied to one side of the upper glass, and the time until the resin composition was completely filled was measured. The flow time measurement result of the resin composition obtained in Example 1 was 90 sec. As the flow time is shorter, the production cycle of the semiconductor device can be shortened, and it is preferably 100 seconds or less in the above test method.

  The resin composition obtained in Example 1 was filled and sealed in a semiconductor device, and the dispersion state evaluation and reliability test of the filler were performed. The components of the semiconductor device used for testing and evaluation are as follows. The chip is a PHASE-2TEG wafer manufactured by Hitachi Ultra LSI Co., with a circuit protection film made of polyimide and a solder bump with Sn / Ag / Cu composition lead-free solder cut to 15mm x 15mm x 0.8mmt. used. The substrate is based on a 0.8mmt glass epoxy substrate equivalent to Hitachi Chemical FR5, and a solder resist PSR4000 / AUS308 made by Taiyo Ink Co., Ltd. is formed on both sides, and a gold-plated pad corresponding to the above solder bump arrangement is arranged on one side. The product 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 the semiconductor device, first apply a uniform flux of about 50 microns on 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 chip with the flux film. After that, the flux is transferred to the solder bump, and then the chip is pressed onto the substrate. A heat treatment was performed in an IR reflow furnace, and solder bumps were melted and produced. The resin composition is filled and sealed by heating the prepared semiconductor device on a hot plate at 110 ° C., applying the resin composition prepared on one side of the chip, filling the gap, and then using a 120 ° C. oven. The resin was heat-cured for a minute to obtain a semiconductor device for evaluation tests.

  As a method for measuring the filler separation phenomenon, the dispersion state of the filler in the resin composition in the semiconductor device is observed and evaluated using an electron microscope (SEM) by cutting and polishing perpendicularly to the chip surface of the prepared semiconductor device. did. In the semiconductor device produced using the resin composition obtained in Example 1, the filler was uniformly present in the resin composition and was in a good dispersion state. The obtained cross-sectional photograph is shown in FIG.

  As a test method for the moisture absorption reflow test, the manufactured semiconductor device was subjected to a JEDEC level 3 moisture absorption treatment (treated at 30 ° C. and 60% relative humidity for 168 hours), followed by IR reflow treatment (peak temperature 260 ° C.) three times. The presence or absence of peeling of the resin composition inside the semiconductor device was confirmed with an ultrasonic flaw detector. In the semiconductor device produced using the resin composition obtained in Example 1, no peeling was observed, and good reliability was shown.

  As the temperature cycle test, the semiconductor device subjected to the above-described moisture absorption reflow test was subjected to a thermal cycle treatment of (−55 ° C./30 minutes) and (125 ° C./30 minutes), and an ultrasonic flaw detector every 250 cycles. The presence or absence of peeling between the chip inside the semiconductor device and the resin composition interface was confirmed. In the semiconductor device produced using the resin composition obtained in Example 1, no peeling was observed, and good reliability was shown. The above results are summarized in Table 1.

(Example 2)
Instead of using 50 parts by weight of bisphenol F-type epoxy resin as epoxy resin (A) and 50 parts by weight of trifunctional glycidylamine, 100 parts by weight of bisphenol F-type epoxy resin is used and aromatic as curing agent (B) Instead of using 50 parts by weight of primary amine curing agent, 39 parts by weight of aromatic primary amine curing agent was used, and spherical synthetic silica (basic silane cup) was used to make the inorganic filler content the same as in Example 1. An experiment was performed in the same manner as in Example 1 except that the amount of the ring-treated product was 286.4 parts by weight, and a resin composition was obtained. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Example 3)
Instead of using 50 parts by weight of aromatic primary amine curing agent as curing agent (B), 33 parts by weight of aromatic primary amine curing agent and 33 parts by weight of aromatic secondary amine curing agent are used for inorganic filling. In order to make the material content the same as in Example 1, an experiment was performed in the same manner as in Example 1 except that spherical synthetic silica (basic silane coupling agent-treated product) was changed to 336.5 parts by weight. Obtained. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

Example 4
As coupling agent (C), instead of using 0.5 part by weight of mercaptosilane coupling agent (acidic), 0.5 part by weight of secondary aminosilane coupling agent (basic) is used as treated silica (D). Example 1 except that 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) was used for 306.8 parts by weight instead of 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product). An experiment was conducted in the same manner as above to obtain a resin composition. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Example 5)
Instead of using 50 parts by weight of bisphenol F-type epoxy resin as epoxy resin (A) and 50 parts by weight of trifunctional glycidylamine, 100 parts by weight of bisphenol F-type epoxy resin is used as the curing agent (B), first grade Instead of using 50 parts by weight of the amine curing agent, 39 parts by weight, and as the coupling agent (C), instead of using 0.5 parts by weight of the mercaptosilane coupling agent (acidic), a secondary aminosilane coupling agent (Basic) 0.5 part by weight,
Instead of using 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) as the treated silica (D), spherical synthetic silica (acidic) was used to make the inorganic filler content the same as in Example 1. An experiment was performed in the same manner as in Example 1 except that 286.4 parts by weight of a silane coupling agent-treated product was used to obtain a resin composition. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Example 6)
Instead of using 50 parts by weight of the aromatic primary amine curing agent as the curing agent (B), coupling is carried out using 33 parts by weight of aromatic primary amine curing agent and 33 parts by weight of aromatic secondary amine type curing agent. Instead of using 0.5 parts by weight of the mercaptosilane coupling agent (acidic) as the agent (C), 0.5 parts by weight of the secondary aminosilane coupling agent (basic) is used, and the treated silica (D) is spherical. Instead of using 306.8 parts by weight of synthetic silica (basic silane coupling agent-treated product), spherical synthetic silica (acidic silane coupling agent-treated product) was used to make the inorganic filler content the same as in Example 1. An experiment was performed in the same manner as in Example 1 except that 336.5 parts by weight were used, and a resin composition was obtained. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Example 7)
In the same manner as in Example 1, a liquid sealing resin composition for underfill was prepared. The evaluation results of the resin composition and the semiconductor device are summarized in Table 2.

(Example 8)
5.7 parts by weight of epoxy silane coupling agent is not added, instead of using 2 parts by weight of diluent as an additive, 6 parts by weight of diluent is used as treated silica (D) and spherical synthetic silica (basic silane) Instead of using 306.8 parts by weight of the coupling agent-treated product, 303.6 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) was used in order to make the inorganic filler content the same as in Example 7. A liquid sealing resin composition for underfill was prepared in the same manner as in Example 1 except that it was used. The evaluation results of the resin composition and the semiconductor device are summarized in Table 2.

(Comparative Example 1)
The same experiment as in Example 1 was conducted except that 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) was used as the treated silica (D) instead of 306.8 parts by weight of spherical synthetic silica. To obtain a resin composition. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1. A cross-sectional photograph of the semiconductor device is shown in FIG.

(Comparative Example 2)
As coupling agent (C), instead of using 0.5 part by weight of mercaptosilane coupling agent (acidic), 0.5 part by weight of secondary aminosilane coupling agent (basic) is used as treated silica (D). In place of using 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product), an experiment was conducted in the same manner as in Example 1 except that 306.8 parts by weight of spherical synthetic silica was used. Got. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Comparative Example 3)
Instead of using 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) as the treated silica (D), 306.8 parts by weight of spherical synthetic silica (acidic silane coupling agent-treated product) were used. Except that, the experiment was performed in the same manner as in Example 1 to obtain a resin composition. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Comparative Example 4)
Example 1 except that 0.5 part by weight of the secondary aminosilane coupling agent (basic) was used as the coupling agent (C) instead of 0.5 part by weight of the mercaptosilane coupling agent (acidic). An experiment was conducted in the same manner to obtain a resin composition. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Comparative Example 5)
Instead of using 0.56.8 parts by weight of the mercaptosilane coupling agent (acidic) as the coupling agent (C) and using 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product), In order to make the inorganic filler content the same as in Example 7, an experiment was conducted in the same manner as in Example 1 except that 305.9 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product) was used. I got a thing. Detailed formulations, resin compositions, and evaluation results of semiconductor devices are summarized in Table 1.

(Comparative Example 6)
Mercaptosilane coupling agent 0.5 parts by weight and epoxy silane coupling agent 5.7 parts by weight were not added, and instead of using 2 parts by weight of diluent as an additive, the diluent was changed to 6 parts by weight. D) Instead of using 306.8 parts by weight of spherical synthetic silica (basic silane coupling agent-treated product), spherical synthetic silica (basic silane cup) was used in order to make the inorganic filler content the same as in Example 7. A liquid sealing resin composition for underfill was prepared in the same manner as in Example 1 except that 302.7 parts by weight of the ring agent-treated product was used. The evaluation results of the resin composition and the semiconductor device are summarized in Table 2.

The terms in Table 1 are explained below.
Bisphenol F-type epoxy resin: EXA-830LVP (Dainippon Ink & Chemicals, epoxy equivalent 161)
Trifunctional glycidylamine: 4- (2,3-epoxypropoxy) -N, N-bis (2,3-epoxypropyl) -2-methylaniline (Sumiepoxy ELM-100, Sumitomo Chemical Co., Ltd., epoxy equivalent 108) )
Aromatic primary amine curing agent: 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Kayahard AA, amine equivalent 65.3)
Aromatic primary amine curing agent: Aromatic primary amine type curing agent T-12 (Sanyo Chemical Industries, amine equivalent 116)
Mercaptosilane coupling agent (acidic) 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-803, molecular weight 196.4, theoretical covering area 398 m ² / g)
Secondary aminosilane coupling agent (basic): N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-573, molecular weight 255.4, theoretical coverage 307 m ² / g)
Primary aminosilane coupling agent (basic): 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-903, molecular weight 179.3, theoretical coating area 436 m ² / g) (actual examples, (Not used in comparative examples)
Epoxysilane coupling agent: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Industrial Co., Ltd. KBM-403, molecular weight 236.3, theoretical coverage 330 m ² / g)
Spherical synthetic silica: Synthetic spherical silica SE-6200 (average particle size 2.5 μm), SO-E3 (average particle size 1 μm), and SO-E2 (average particle size 0.5 μm) manufactured by Admatechs Co., Ltd. 45:40 : Blended at a weight ratio of 15 Spherical synthetic silica (basic silane coupling agent treated product): Spherical synthetic silica sprayed with 0.3% by weight of secondary aminosilane coupling agent Low stress agent : Epoxy-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., E-1800-6.5, number average molecular weight 1800, epoxy equivalent 250)
Diluent: ethylene glycol mono-normal-butyl ether acetate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
Pigment: Carbon black pigment (Mitsubishi Chemical, MA-600)

In Table 1, in Examples 1 to 3 in which the acidic coupling agent and the basic treated silica are combined, even if the composition of the epoxy resin (A) and the curing agent (B) is changed, high fluidity is exhibited, and the filler separation phenomenon is I couldn't see it. 1 that is a cross-sectional photograph of Example 1, it can be seen that the underfill (the resin composition of the present invention) is uniformly filled. The same results were obtained in Examples 4 to 6 in which a basic coupling agent and acidic treated silica were combined.
Next, in the case of a combination of an acidic coupling agent and untreated silica (Comparative Example 1) and a combination of a basic coupling agent and untreated silica (Comparative Example 2), the viscosity slightly increases and the flow time is long. A filler separation phenomenon was observed. When FIG. 2 which is a cross-sectional photograph of the comparative example 1 is seen, a portion 6 where the filler settles on the upper part of the underfill and becomes only the resin can be observed black.
In the combination of the acidic coupling agent and the acid-treated silica (Comparative Example 3), and the combination of the basic coupling agent and the basic-treated silica (Example 4), the flow time cannot be measured due to poor filling, and it depends on the semiconductor device Observation of the filler separation phenomenon and reliability test evaluation could not be carried out.
In Comparative Example 5 where neither acidic nor basic coupling agents were used as coupling agents, filler separation was not observed, but minute peeling was observed in the moisture absorption reflow test, and further peeling after the temperature cycle test. Progress was observed. Such peeling becomes a problem because it reduces the operational reliability of the semiconductor device.

  In Table 2, in Example 7 where a mercaptosilane coupling agent, an epoxy silane coupling agent, and spherical synthetic silica (basic silane coupling agent-treated product) were combined, high fluidity was exhibited and no filler separation phenomenon was observed. It was. Furthermore, no peeling was observed even after the moisture absorption reflow test and temperature cycle test (1000 cycles) of the semiconductor device, and the semiconductor device showed good reliability. In the adhesion test between the resin composition of Example 7 and the substrate, the failure mode was internal destruction of the substrate layer, and the interface adhesion between the resin composition and the substrate was good. In addition, it carried out in the following procedures as adhesive strength-organic substrate. A resin composition is applied to the surface on which a solder resist (PSR-4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) is formed on an FR5-equivalent glass epoxy substrate, and polyimide (CR-6061 manufactured by Sumitomo Bakelite) is formed on the resin composition The 2 mm × 2 mm square silicon chip was mounted so that the PI surface was in contact with the resin composition, and cured at 150 ° C. for 120 minutes to prepare a test piece. While installing and heating the test piece on a 260 ° C. hot plate, a die shear strength test was performed using an automatic mount measuring device (BT4000 manufactured by DAGE), and the fracture site after the test was visually confirmed.

In Example 8 in which no epoxysilane coupling agent was added, relatively good fluidity was exhibited, and no filler separation phenomenon was observed. In addition, since the failure mode in the adhesion test of the resin composition of Example 8 was observed to peel at the interface between the substrate surface layer and the resin composition, the adhesion with the substrate surface layer was lower than that in Example 7. It was. The semiconductor device filled and sealed with Example 8 did not show peeling even after the moisture absorption reflow test and the temperature cycle test (1000 cycles), and showed good reliability.
In Comparative Example 6 in which the mercaptosilane coupling agent and the epoxysilane coupling agent were not added, the fluidity was low and a filler separation phenomenon was observed. Further, in the fracture mode after the adhesion test of the resin composition of Comparative Example 6, peeling at the PI surface layer-resin composition interface was observed, and the adhesion with the PI surface was low. In the semiconductor device filled and sealed with Comparative Example 6, peeling was not observed in the moisture absorption reflow test, but peeling was further observed after the temperature cycle test (600 cycles). Such peeling becomes a problem because it reduces the operational reliability of the semiconductor device.

  INDUSTRIAL APPLICATION This invention is used suitably for the liquid sealing resin composition for underfill which a crack, the stress of curvature, etc. do not generate | occur | produce easily, the semiconductor device using the same, and its assembly method.

FIG. 1 shows a cross-sectional photograph of the semiconductor device of Example 1. FIG. 2 shows a cross-sectional photograph of the semiconductor device of Comparative Example 1.

Explanation of symbols

1 Solder bump (95% tin / 5% silver)
2 Silicon chip 3 Underfill 4 Gold pad 5 Solder resist 6 Part with a lot of resin made by separation and sedimentation of filler and little silica

Claims (6)

(A) epoxy resin,
(B) a curing agent,
(C) a first silane coupling agent, and
(D) an inorganic filler in which the second silane coupling agent is chemically modified on the surface layer;
A liquid encapsulating resin composition for underfill comprising:
One acidic group of the first silane coupling agent and a second silane coupling agent and the other have a basic group,
The acidic group is a thiol group or a functional group that thermally decomposes to generate a thiol group,
The basic group is an amino group or a functional group that thermally decomposes to generate an amino group, and the silane coupling agent having the basic group is a secondary aminosilane coupling agent. Liquid sealing resin composition for fill.   Furthermore, (E) 3rd coupling agent is mix | blended, The said (E) 3rd coupling agent contains either an epoxy silane coupling agent or an acrylic silane coupling agent, The under of Claim 1 Liquid sealing resin composition for fill. The first silane coupling agent is a silane coupling agent having the acidic group; and
The liquid sealing resin composition for underfill according to claim 1 or 2, wherein the second silane coupling agent is the secondary aminosilane coupling agent having the basic group . The first silane coupling agent is the secondary aminosilane coupling agent having the basic group , and
The second coupling agent is, the a silane coupling agent that having a acidic group claim 1 or 2 underfill liquid sealing resin composition. A substrate, a chip disposed on the substrate, and an underfill filling the gap between the two,
A semiconductor device in which the underfill is obtained by curing the liquid sealing resin composition for underfill according to any one of claims 1 to 4. A method of manufacturing a semiconductor device comprising a substrate, a chip disposed on the substrate, and an underfill filling the gap between the two,
(I) a step of filling the gap between the substrate and the chip with the liquid sealing resin composition for underfill according to any one of claims 1 to 4;
(II) a step of curing the filled underfill liquid sealing resin composition to form an underfill;
A method of manufacturing a semiconductor device including: