JP2008013710A - Resin composition, sealing material, semiconductor device and method for producing the semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic filler-containing resin composition enabling a semiconductor element and a substrate to be joined to each other owing to the semiconductor element's own weight even in case of being used as a nonflow-type underfilling material. <P>SOLUTION: The resin composition, to be used for sealing up a semiconductor element and a substrate together, comprises a first epoxy resin liquid at room temperature, a second epoxy resin higher in cure-starting temperature than the first epoxy resin, a silicone-modified epoxy resin and an inorganic filler. A sealing material comprising this resin composition is provided. A semiconductor device is also provided, being such that a semiconductor element and a substrate are sealed up together via the sealing material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, a sealing material, a semiconductor device, and a method for manufacturing a semiconductor device.

  2. Description of the Related Art In recent years, technological innovations for making semiconductor packages lighter and thinner have been remarkable, and various package structures using a flip chip method have been proposed and commercialized.

  The flip chip method in which a protruding electrode or the like is directly provided on the circuit surface of a semiconductor element and the semiconductor element and the substrate are directly connected is one of the methods that can minimize the semiconductor package. In such flip chip type semiconductor packages, the bonding between the semiconductor element and the substrate is often connected using solder bumps, and the sealing resin is interposed in the gap between the semiconductor element and the substrate in the connection using the solder bumps. This improves the connection reliability of the solder bumps.

  As one of sealing methods for providing a sealing resin between the semiconductor element and the substrate, a no-flow type underfill material (NUF) has been proposed. This NUF is a method in which a resin is directly applied to a substrate, a semiconductor element having solder bumps is mounted thereon, and solder bonding and resin sealing are simultaneously performed (see, for example, Patent Document 1).

  In this sealing method using NUF, since the solder connection is performed using a conveyor-type heating furnace called a reflow apparatus, the semiconductor element and the circuit board are joined by the weight of the semiconductor element. In recent years, a high degree of reliability has been required for NUF, and NUF including an inorganic filler has been studied (for example, see Patent Document 2). However, when NUF containing an inorganic filler is soldered using a conveyor-type heating furnace, the addition of the inorganic filler increases the viscosity of the sealing resin, making it difficult to connect to the substrate due to the weight of the semiconductor element. It was. Therefore, in many cases, it has been unavoidable to take a solder connection method by a so-called local reflow mounting method of a heat-compression type.

US Pat. No. 5,128,746 JP2003-301026A

  An object of the present invention is to provide a resin composition capable of connecting a semiconductor element and a substrate by its own weight even when a resin composition containing an inorganic filler is used as a no-flow type underfill material. There is.

（１０）前記無機充填材の含有量は、前記樹脂組成物全体の８０重量％以下である上記（１）ないし（９）のいずれかに記載の樹脂組成物。
（１１）上記（１）ないし（１０）のいずれかに記載の樹脂組成物で構成されていることを特徴とする封止材。
（１２）上記（１１）に記載の封止材で、半導体素子と基板との間が封止されていることを特徴とする半導体装置。
（１３）基板の半導体素子が搭載される部分に上記（１）ないし（１０）のいずれかに記載の樹脂組成物を塗布する塗布工程と、半導体素子を搭載し、仮圧着する仮圧着工程と、前記樹脂組成物を硬化する硬化工程とを有していることを特徴とする半導体装置の製造方法。 Such an object is achieved by the present invention described in the following (1) to (13).
(1) A resin composition used for sealing between a semiconductor element and a substrate, which is a first epoxy resin that is liquid at room temperature, a second epoxy resin that has a higher curing start temperature than the liquid resin, and silicone A resin composition comprising a modified epoxy resin and an inorganic filler.
(2) The resin composition according to (1), wherein the second epoxy resin contains a diallyl bisphenol type epoxy resin.
(3) The resin composition according to (2), wherein the diallyl bisphenol type epoxy resin is a diallyl bisphenol A type epoxy resin.
(4) The resin composition according to any one of (1) to (3), further including a curing agent.
(5) The resin composition according to (4), wherein the curing agent includes a first curing agent and a second curing agent having a melting point different from that of the first curing agent.
(6) The resin composition according to (5), wherein the difference between the melting point of the first curing agent and the melting point of the second curing agent is 30 ° C. or higher.
(7) The resin composition according to (5) or (6), wherein at least one of the first curing agent and the second curing agent is a curing agent having flux activity.
(8) The resin composition according to the above (7), wherein the curing agent having flux activity is a compound containing at least two phenolic hydroxyl groups and a carboxyl group directly bonded to an aromatic group in one molecule.
(9) The said silicone modified epoxy resin is a resin composition in any one of said (1) thru | or (8) which is shown by following formula (1).

(10) The resin composition according to any one of (1) to (9), wherein the content of the inorganic filler is 80% by weight or less of the entire resin composition.
(11) A sealing material comprising the resin composition according to any one of (1) to (10) above.
(12) A semiconductor device, wherein the gap between the semiconductor element and the substrate is sealed with the sealing material according to (11).
(13) An application step of applying the resin composition according to any one of (1) to (10) above on a portion of the substrate on which the semiconductor element is mounted, a temporary pressure bonding step of mounting the semiconductor element and temporarily pressing it. And a curing step of curing the resin composition.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the resin composition containing an inorganic filler is used as a no-flow type underfill material, the resin composition which can connect a semiconductor element and a board | substrate with the dead weight of a semiconductor element can be provided. .
Further, when a curing agent having flux activity is used as the curing agent, connection reliability can be particularly improved.

Hereinafter, the resin composition, the sealing material, the semiconductor device, and the method for manufacturing the semiconductor device of the present invention will be described in detail.
The resin composition of the present invention is a resin composition used for sealing between a semiconductor element (chip) and a substrate, and is cured from a first epoxy resin that is liquid at room temperature and the first epoxy resin. It includes a second epoxy resin having a high temperature, a silicone-modified epoxy resin, and an inorganic filler.
Moreover, the sealing material of this invention is comprised by the resin composition as described above, It is characterized by the above-mentioned.
In addition, a semiconductor device of the present invention is characterized in that the gap between the semiconductor element and the substrate is sealed with the sealing material described above.
Further, the method for manufacturing a semiconductor device of the present invention includes a coating step of applying the resin composition described above on a portion of the substrate on which the semiconductor element is mounted, a temporary pressing step of mounting the semiconductor element and temporarily pressing it, And a curing step for curing the resin composition.

First, the resin composition will be described.
The resin composition includes a first epoxy resin that is liquid at room temperature. Thereby, a resin composition can be made into a liquid state and application | coating to a board | substrate can be made easy.
As the first epoxy resin, any one having two or more epoxy groups in one molecule and being liquid at room temperature (for example, 25 ° C.) can be used. Resin, bisphenol F type epoxy resin such as bisphenol F type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolak type epoxy resin, triphenolalkane such as triphenolmethane type epoxy resin, triphenolpropane type epoxy resin Type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, cyclopentadiene type epoxy resin and the like. These epoxy resins can be used individually by 1 type or in mixture of 2 or more types. Among these first epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable. Thereby, a liquid and low-viscosity product can be obtained, and workability can be improved.

  Although content of the said 1st epoxy resin is not specifically limited, 5 to 50 weight% of the whole said resin composition is preferable, and 10 to 40 weight% is especially preferable. If the content is less than the lower limit, the fluidity may be too high and the resin composition may protrude when the semiconductor element and the substrate are joined. If the content exceeds the upper limit, the fluidity is too low and the fluidity is reduced. Application may be difficult.

The resin composition includes a second epoxy resin having a curing start temperature higher than that of the first epoxy resin. Thereby, the viscosity of the resin composition during reflow can be adjusted, and the stability of solder connection can be ensured.
The second epoxy resin is not particularly limited as long as it has a higher curing start temperature than the first epoxy resin. For example, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cresol naphthol type epoxy resin, a biphenyl type Examples include epoxy resins having an allyl group, such as epoxy resins, biphenylaralkyl type epoxy resins, naphthalene skeleton type epoxy resins, diallyl bisphenol A type epoxy resins, diallyl bisphenol F type epoxy resins and the like.
Among these, an epoxy resin having an allyl group (particularly diallyl bisphenol A type epoxy resin) is preferable. Thereby, the adjustment of the curing characteristics of the resin composition can be facilitated, whereby the semiconductor element and the substrate can be bonded even with a normal reflow temperature profile.

  The difference between the curing start temperature of the first epoxy resin and the curing start temperature of the second epoxy resin is not particularly limited, but is preferably 30 ° C. or higher, and particularly preferably 50 ° C. or higher. When the temperature difference is within the above range, the flux activity is excellent particularly from a low temperature region.

In addition, the curing start temperature of the second epoxy resin is preferably 130 ° C. or higher, and particularly preferably 160 ° C. or higher. Thereby, it is possible to suppress the progress of curing during the solder reflow, particularly during the soak temperature and the soak time in the surface mounting profile (generally, the region causing the flux activity, for example, the region (a) in FIG. 1).
The curing start temperature can be evaluated based on the onset temperature of a chart obtained by performing measurement under a composition mixing condition to be used, for example, using DSC.

  Although content of the said 2nd epoxy resin is not specifically limited, 0.1 to 40 weight% of the whole said resin composition is preferable, and 1 to 20 weight% is especially preferable. When the content exceeds the upper limit, the reactivity of the resin composition as a whole is lowered, and cured product characteristics, particularly thermal properties may be impaired. When the content is less than the lower limit, the effect of adjusting the curing start temperature is achieved. May decrease.

The resin composition includes a silicone-modified epoxy resin. Thereby, the wettability between the resin composition and the substrate or the semiconductor element can be improved, and thereby the semiconductor element and the substrate are bonded by the weight of the semiconductor element even if the resin composition contains the inorganic filler. be able to.
Examples of the silicone-modified epoxy resin include silicone-modified (liquid) epoxy resins having a disiloxane structure, and specifically, silicone-modified epoxy resins represented by the following general formula (1).

  The silicone modification rate of the silicone-modified epoxy resin is not particularly limited, but m of the silicone-modified resin is preferably 5 or less, and particularly preferably m is 1 or less. When the modification rate is within the above range, wettability with an organic compound such as a solder resist film provided on a substrate, a buffer film of a circuit provided on a semiconductor element, etc. Excellent).

  More specifically, the silicone-modified epoxy resin includes a silicone-modified liquid epoxy resin in which m of the silicone-modified liquid epoxy resin represented by the general formula (1) is 0, and a phenol represented by the following general formula (2). It is preferable that these are synthesized by heating reaction. Thereby, the wettability with respect to a board | substrate, a semiconductor element, etc. can be improved.

  The molar ratio of the silicone-modified liquid epoxy resin represented by the general formula (1) in which m is 0 and the phenols represented by the general formula (2) (epoxy of the silicone-modified epoxy resin) (Group molar ratio / hydroxyl molar ratio of phenols) is not particularly limited, but is preferably 1 to 10, and particularly preferably 1 to 5. When the molar ratio is within the above range, the yield of the reaction product and low volatility are particularly excellent.

  Although content of the said silicone modified epoxy resin is not specifically limited, 0.1 to 20 weight% of the whole said resin composition is preferable, and 0.5 to 5 weight% is especially preferable. If the content exceeds the upper limit, cured product properties, particularly thermal properties such as glass transition temperature, may be reduced, and if it is less than the lower limit, the effect of improving wettability may be reduced.

The resin composition preferably includes a curing agent to cure the epoxy resin. Examples of the curing agent include a polyaddition type curing agent, a catalyst type curing agent, a condensation type curing agent, and a curing agent having flux activity.
Furthermore, it is preferable that the said hardening | curing agent contains the 1st hardening | curing agent and the 2nd hardening | curing agent in which a kind differs from the said 1st hardening | curing agent, More specifically, a 1st hardening | curing agent, a said 1st hardening | curing agent, It is preferable to contain the 2nd hardening | curing agent from which melting | fusing point differs. Thereby, adjustment of the hardening start temperature of the said epoxy resin can be made easy.

  The difference between the melting point of the first curing agent and the melting point of the second curing agent is not particularly limited, but is preferably 30 ° C. or higher, and particularly preferably 50 to 120 ° C. When the difference in melting point is within the above range, the flux activity particularly from the low temperature region is excellent, thereby improving the oxide film removal efficiency.

  Examples of such a curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diamino. In addition to aromatic polyamines such as diphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydralazide, and the like, alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), and methyltetrahydrophthalic anhydride (MTHPA) Products, acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), novolac type phenolic resin, phenolic Polyphenol compounds such as mer, polymercaptan compounds such as polysulfide, thioester, thioether, isocyanate compounds such as isocyanate prepolymers, blocked isocyanates, polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins, benzyldimethylamine (BDMA), tertiary amine compounds such as 2,4,6-trisdimethylaminomethylphenol (DMP-30), imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24), BF3 complex Condensation type hardeners such as catalyst type curing agents such as Lewis acids, phenolic resins such as resol type phenolic resins, urea resins such as methylol group-containing urea resins, melamine resins such as methylol group-containing melamine resins, etc. Agents. These curing agents can be used alone or in combination of two or more depending on the type of epoxy resin used and the properties of the desired cured product.

  Although content of the said 1st hardening | curing agent is not specifically limited, 1-30 weight% of the whole said resin composition is preferable, and 5-15 weight% is especially preferable. Moreover, although content of the said 2nd hardening | curing agent is not specifically limited, 0.1 to 10 weight% of the whole said resin composition is preferable, and 0.5 to 5 weight% is especially preferable. When the content is within the above range, the cured product property balance of thermal properties such as glass transition temperature and mechanical properties such as elastic modulus is excellent.

  Moreover, it is preferable that at least one of the first curing agent and the second curing agent is a curing agent having a flux activity, and in particular, both the first curing agent and the second curing agent have a flux activity. It is preferable that As a result, the oxide film of the lead-free type solder that has become stricter has a sufficient removing action. Furthermore, since the curing agent having flux activity is reactive with the epoxy resin, the outgas is reduced, the contamination of the electronic component can be reduced, and the action as an ionic impurity can be reduced, thereby preventing the conductive member from being corroded. be able to.

  The curing agent having a flux activity used in the present invention has an action of reducing an oxide film on the surface of a solder bump provided on a semiconductor element (semiconductor chip) to such an extent that it can be electrically bonded to a substrate, and an epoxy resin. Is a compound having a functional group that reacts with.

  Such a flux activator is not particularly limited, but preferably contains a first flux curing agent having flux activity and a second flux curing agent having flux activity and different from the first flux curing agent. . Thereby, the timing of flux activity can be adjusted.

  The first flux activator is, for example, an epoxy resin curing agent containing at least two phenolic hydroxyl groups and at least one aromatic carboxyl group in one molecule, specifically 2,3-dihydroxy. Benzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid, 1,4-dihydroxy-2-naphthoic acid, 3 , 5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, phenolphthalin, diphenolic acid and the like. These can be added alone or in combination. It is a condition for utilizing in this invention that all have a flux effect | action. Moreover, since these compounds all easily absorb moisture and cause voids, it is preferable to dry them in advance. Among these, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and 3,4-dihydroxybenzoic acid are preferable. Thereby, hardened | cured material characteristic can be improved, having flux activity.

  The second flux curing agent is different from the first flux curing agent and contains at least two carboxyl groups in one molecule. Examples of the second flux curing agent include o-phthalic acid, trimellitic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, 4-hydroxy (o-phthalic acid), 3-hydroxy (o-phthalic acid), Tetrahydrophthalic acid, maleic acid, and those containing an alkylene group include succinic acid, malonic acid, glutaric acid, malic acid, sebacic acid, adipic acid, azelaic acid, suberic acid, pimelic acid, 1,9-nonanedicarboxylic acid, dodecane A diacid etc. are mentioned. These may be used alone or in combination. Among these, sebacic acid is preferable. Thereby, the flux effect can be exhibited from a lower temperature region.

  The melting point of the first flux curing agent is preferably higher than the melting point of the second flux curing agent. Thereby, a 2nd flux hardening | curing agent can melt | dissolve in an epoxy resin at lower temperature. As it dissolves, the oxide film on the solder surface is removed by the action of carboxylic acid. Subsequently, when the second flux curing agent is dissolved, the melting temperature of the first flux curing agent in the epoxy resin can be further lowered. For this reason, it becomes possible to improve the wettability to the solder and make the reaction uniform.

  Further, the difference between the melting point of the first flux curing agent and the melting point of the second flux curing agent is preferably 30 ° C. or more, and particularly preferably 50 to 120 ° C. If the difference in melting point is less than the lower limit value, the flux activity may be difficult to develop, and if the upper limit value is exceeded, the reaction of the epoxy resin occurs at an early stage. There may be problems with connectivity.

  Although content of the said 1st flux hardening | curing agent is not specifically limited, 1-30 weight% of the whole said resin composition is preferable, and 5-15 weight% is especially preferable. When the content is within the above range, the cured product properties such as glass transition temperature and elastic modulus are excellent while maintaining high flux activity.

  Moreover, although content of the said 2nd flux hardening | curing agent is not specifically limited, 0.1 to 10 weight% of the whole said resin composition is preferable, and 0.5 to 5 weight% is especially preferable. When the content is within the above range, the cured product property balance of thermal properties such as glass transition temperature and mechanical properties such as elastic modulus is excellent.

  The ratio of the content of the first flux curing agent and the second flux curing agent (first flux curing agent / second flux curing agent) is not particularly limited, but may be 0.01 to 0.5. Particularly preferred is 0.03 to 0.4, and most preferred is 0.05 to 0.3. When the ratio is less than the lower limit value, it may be difficult to continuously exhibit the flux activity, and when the ratio exceeds the upper limit value, the moisture resistance of the cured product may be reduced.

The resin composition includes an inorganic filler. Thereby, the difference in thermal expansion coefficient between the sealing material and the semiconductor element can be reduced, and thereby the connection reliability of the sealing material can be improved.
Examples of the inorganic filler include silicates such as talc, calcined clay, and mica, oxides such as alumina, silica, and fused silica, carbonates such as calcium carbonate and hydrotalcite, aluminum hydroxide, magnesium hydroxide, and the like. Hydroxides, sulfates such as barium sulfate and calcium sulfite or sulfites, borates such as zinc borate, nitrides such as aluminum nitride and silicon nitride, and the like. These may be used alone or in combination. Among these, silica is preferable. Thereby, the inorganic filler excellent in purity can be obtained easily. Furthermore, the connection reliability is particularly excellent.

  Although content of the said inorganic filler is not specifically limited, It is preferable that it is 80 weight% or less of the whole said resin composition, and 10 to 70 weight% is especially preferable. If the content is less than the lower limit, the effect of improving connection reliability may be reduced, and if the content exceeds the upper limit, it may be difficult to spread the resin composition. Furthermore, when the content is within the above range, the balance of characteristics (humidity resistance, workability, etc.) as the resin composition is particularly excellent.

  The shape of the inorganic filler is not particularly limited, and may be a crushed inorganic filler or a spherical inorganic filler, but is preferably a spherical inorganic filler. Thereby, damage to the surface of the semiconductor element can be reduced.

  The particle size of the inorganic filler is not particularly limited, but is preferably 6 μm or less in average particle size and 30 μm or less in maximum particle size, particularly 1 μm or less in average particle size and 5 μm or less in maximum particle size. It is preferable that When the particle size is within the above range, the possibility of causing connection failure due to the inorganic filler during solder bonding is reduced.

  It is preferable to add a curing accelerator to the resin composition in order to accelerate the curing reaction of the epoxy resin. Examples of the curing accelerator include imidazole compounds, organic phosphines such as triphenylphosphine and methyldiphenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, and tetraphenylphosphonium / tetranaphthoic acid borate. And tetraphenylphosphonium / tetranaphthyloxyborate, tetrasubstituted phosphonium / tetrasubstituted borate such as tetraphenylphosphonium / tetranaphthyloxyborate, adducts of phosphine compounds and quinone compounds, and the like. Among these, it is preferable to use together an imidazole compound and an adduct of a phosphine compound and a quinone compound. Thereby, in addition to being able to control the reactivity of a resin composition easily, the void of the sealing material finally obtained can be reduced.

  Examples of the imidazole compound include diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof, amine compounds such as tributylamine and benzyldimethylamine, and 2-methylimidazole. Can be mentioned.

Examples of the adduct of the phosphine compound and the quinone compound include phosphine compounds such as triphenylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, and tributylphosphine, and 1,4-benzoquinone, methyl- Examples include adducts with quinone compounds such as 1,4-benzoquinone, methoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and 1,4-naphthoquinone. Of these adducts of phosphine compounds and quinone compounds, adducts of triphenylphosphine and 1,4-benzoquinone are preferred.
Examples of a method for producing such an adduct of a phosphine compound and a quinone compound include a method of isolating the phosphine compound and quinone compound used as raw materials by addition reaction in an organic solvent in which both are dissolved. . The adduct of a phosphine compound and a quinone compound may be used individually by 1 type, or may be used in combination of 2 or more type.

  In addition to the epoxy resin, the inorganic filler, and the like, the resin composition includes additives such as a reactive diluent, a pigment, a dye, a leveling agent, an antifoaming agent, a low stress agent, and a coupling agent as necessary. It is also possible to use. Any of these additives should not cause voids, so it is preferable to add them after confirming heat resistance, volatility, wettability to the substrate, and the like.

In addition, the resin composition preferably contains a compound having a flux action when a normal curing agent having no flux function is used as the curing agent.
Moreover, you may use together the hardening | curing agent which has a flux function, and the compound which has a flux effect | action.

  By using the above resin composition, for example, even when solder reflow is performed with a normal temperature profile as shown in FIG. 1, the semiconductor element and the substrate can be easily joined. That is, in the conventional sealing resin composition, the curing reaction proceeds due to the heating in the region of FIG. 1A, and the viscosity of the resin composition is increased. Due to this increase in viscosity, a layer of the resin composition is formed on the pad of the substrate, and even if the solder bump melts, it cannot be connected to the pad, resulting in poor connection. On the other hand, in the resin composition of the present invention, since the reaction of the resin composition in the region of FIG. 1 (a) can be suppressed, the viscosity of the resin composition is not increased, thereby improving the solder bump and the pad. It became possible to connect to. Furthermore, since the reactivity of the epoxy resin can be suppressed, the reaction of the functional group exhibiting the flux activity is also suppressed, whereby the flux activity can be expressed over a long period of time. Therefore, it is possible to further promote the removal of the oxide film of the solder bump and further improve the connectivity.

  A resin composition for sealing can be obtained by mixing such a resin composition using, for example, three rolls at room temperature and vacuum degassing.

Next, a sealing material, a semiconductor device, and a method for manufacturing the semiconductor device will be described.
FIG. 2 is a schematic diagram illustrating a process for manufacturing a semiconductor device using the above resin composition.
As shown in FIG. 2A, a substrate 1 provided with a pad portion 11 is prepared.
Next, the above resin composition is applied to the upper side of the pad portion 11 (upper side in FIG. 2), and the syringe 12 is applied to obtain the resin composition 2 applied in an X shape (application process, FIG. 2B). )). In this state, the resin composition 2 is in an uncured state. Examples of the method for applying the resin composition 2 include a dispensing method and a printing method.
Next, the semiconductor element 3 having the solder bumps 31 is aligned using the flip chip bonder 32 and mounted on the pad portion 11 (temporary pressure bonding step, FIG. 2C). At this time, the resin composition 2 is slightly wet and spread as compared with the case where the resin composition 2 is applied on the pad portion 11. Even in this state, the resin composition 2 is uncured.
Then, the substrate 1 on which the semiconductor element 3 is mounted is passed through the solder reflow furnace 4 and the semiconductor element 3 and the substrate 1 are soldered (curing step, FIG. 2D). At this time, although the resin composition 2 contains an inorganic filler, the semiconductor element 3 can be soldered by its own weight. As described above, since the solder connection can be performed by the conveyor type solder reflow furnace 4, productivity can be improved by using the resin composition 2.
After passing through the solder reflow furnace 4, the resin composition 2 is cured and finally becomes a sealing material 2 ′ for sealing between the semiconductor element 3 and the substrate 1. In addition, an after baking process may be provided after a hardening process as needed, and a hardening degree may be accelerated | stimulated.

In the semiconductor device 10 obtained through such steps, the space between the substrate 1 and the semiconductor element 3 is sealed with a sealing material 2 ′ (FIG. 2E).
As the semiconductor device 10, for example, a gap between a semiconductor element (semiconductor package) such as a flip chip or a CSP (chip size package) and a substrate can be sealed. In particular, in the resin composition 2 using the curing agent having flux activity, for example, the resin composition 2 is directly applied to the substrate 1 without adding the flux, and the semiconductor element 3 having the solder bumps 31 is applied from above the substrate 1. It can be used as a no-flow type underfill material that performs solder bonding and resin sealing simultaneously by mounting and heat curing. It is also possible to apply the resin composition 2 on the solder bump 31 side of the semiconductor element 3 having the solder bumps 31 and mount the resin composition 2 on the substrate 1 to perform solder bonding and resin sealing at the same time.

Hereinafter, the present invention will be described in detail based on examples and comparative examples.
(Example 1)
1. Manufacture of resin composition for sealing 28.1 wt% of bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin and diallyl as the second epoxy resin Bisphenol A type epoxy resin (Nippon Kayaku Co., Ltd., RE-810NM, epoxy equivalent 210) 9.3% by weight, silicone modified epoxy resin (Toshiba Silicone Co., Ltd., TSL-9906) and bisphenol Gentisic acid (manufactured by Midori Chemical Co., Ltd., gentidine) previously dried in vacuum at 130 ° C. and 5 torr as a first curing agent (first flux active curing agent), 1.9 wt% of 5: 1 reactant of A The acid “2,5-dihydroxybenzoic acid”, melting point 202 ° C., 7.5% by weight and the second curing agent (second flux) As an active curing agent), sebacic acid (Tokyo Chemical Industry Co., Ltd., sebacic acid, melting point: 134 ° C.) 1.9% by weight previously dried at 80 ° C. and 5 torr for 3 hours in advance, and 2-phenyl-4 as a curing accelerator -0.05% by weight of methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., 2P4MZ), 0.15% by weight of an adduct of triphenylphosphine and 1,4-benzoquinone, acrylonitrile butadiene rubber (Ube) as a stress reducing material Kosan Co., Ltd., CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber (1.1% by weight) and silica as an inorganic filler (manufactured by Admatechs Co., Ltd., SO-25H, average particle diameter 0.7 μm) 50.0% % Was dispersed and kneaded at room temperature with three rolls and defoamed under vacuum to obtain a sealing resin composition.
The difference in melting point between the first curing agent and the second curing agent was 68 ° C.

2. Manufacture of semiconductor device The above resin composition for sealing is applied in an X shape to a connection pad portion of a circuit board (BT (bismaleimide / triazine) resin substrate, connection pad, surface is gold-plated), and a flip chip bonder from above. Semiconductor elements (solder: tin-silver, melting point: 221 ° C., bump number: 900 bumps, bump height: 80 μm, semiconductor element size: 10 mm square, passivation: polyimide, chip thickness while positioning using : 525 μm).
Next, after melting and connecting the solder using the reflow heating furnace having the temperature profile shown in FIG. 1, the sealing resin was cured at 150 ° C. for 90 minutes as post-curing to obtain a semiconductor device.

(Example 2)
Example 1 was repeated except that the first epoxy resin was changed to the following.
As the first epoxy resin, bisphenol F type epoxy resin (Dainippon Ink Chemical Co., Ltd., EXA-830LVP, epoxy equivalent 161) 22.5% by weight and naphthalene type tetrafunctional epoxy resin (Dainippon Ink Chemical Co., Ltd.) ), Product number HP-4700) A 5.6 wt% melt mixture was used.

(Example 3)
The following was used as the first curing agent, and the same procedure as in Example 1 was performed except that the sealing resin composition was blended as follows.
Bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 27.1% by weight and diallyl bisphenol A type epoxy resin (Nippon Kay) as the second epoxy resin. Yakuhin Co., Ltd., RE-810NM, epoxy equivalent 210) 9.0% by weight, 5: 1 reaction product of silicone compound (TSL-9906 made by Toshiba Silicone Co., Ltd.) and bisphenol A as silicone-modified epoxy resin 1.8% by weight, phenol phthaline (manufactured by Tokyo Chemical Industry Co., Ltd., phenol phthaline, melting point 235 ° C.) previously vacuum-dried at 130 ° C. and 5 torr as a first curing agent (first flux active curing agent) ) 9.0% by weight and a second curing agent (second flux active curing agent) at 80 ° C. and 5 torr in advance. 1.8% by weight of sebacic acid (Tokyo Kasei Kogyo Co., Ltd., sebacic acid, melting point 134 ° C.) dried for 3 hours under vacuum, and 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator 2P4MZ) 0.05% by weight, adduct of triphenylphosphine and 1,4-benzoquinone 0.15% by weight, acrylonitrile butadiene rubber (manufactured by Ube Industries Co., Ltd., CTBN1008SP, carboxyl group terminal) 1.1 wt% of butadiene acrylic rubber) and 50.0 wt% of silica (manufactured by Admatechs Co., Ltd., SO-25H, average particle size 0.7 μm) as an inorganic filler at room temperature with three rolls The resin composition for sealing was obtained by dispersing and kneading and defoaming under vacuum.
The difference in melting point between the first curing agent and the second curing agent was 101 ° C.

Example 4
The following was used as the first curing agent, and the same procedure as in Example 1 was performed except that the sealing resin composition was blended as follows.
Bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 27.1% by weight and diallyl bisphenol A type epoxy resin (Nippon Kay) as the second epoxy resin. Yakuhin Co., Ltd., RE-810NM, epoxy equivalent 210) 9.0% by weight, 5: 1 reaction product of silicone compound (TSL-9906 made by Toshiba Silicone Co., Ltd.) and bisphenol A as silicone-modified epoxy resin 1.8% by weight and 1,1,1, -tris (p-hydroxyphenyl) ethane (manufactured by Triquest Japan, product number THPE-E, previously vacuum-dried at 130 ° C. and 5 torr as a first curing agent for 3 hours. (Melting point 246 ° C.) 7.2% by weight and 80 ° C. in advance as the second curing agent (second flux active curing agent), 3.6% by weight of sebacic acid (Tokyo Kasei Kogyo Co., Ltd., sebacic acid, melting point 134 ° C.), which was vacuum-dried for 3 hours at torr, and 2-phenyl-4-methylimidazole (Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator 2P4MZ) 0.05% by weight, adduct of triphenylphosphine and 1,4-benzoquinone 0.15% by weight, acrylonitrile butadiene rubber (Ube Industries, CTBN1008SP, carboxyl) as a stress reducing material 3 rolls containing 1.1% by weight of base terminal butadiene acrylic rubber and 50.0% by weight of silica (manufactured by Admatechs Co., Ltd., SO-25H, average particle size 0.7 μm) as an inorganic filler. The resin composition for sealing was obtained by dispersing and kneading at room temperature and defoaming under vacuum.
The difference in melting point between the first curing agent and the second curing agent was 112 ° C.

(Example 5)
The following were used as the first curing agent and the second curing agent, the flux compound was further blended, and the sealing resin composition was blended in the same manner as in Example 1 except for the following.
Bisphenol F type epoxy resin (Dainippon Ink Chemical Industries, Ltd., EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 26.1% by weight, diallyl bisphenol A type epoxy resin (Nipponization) as the second epoxy resin 8.7% by weight of RE-810NM, epoxy equivalent 210) manufactured by Yakuhin Co., Ltd., and 5: 1 reaction product of silicone compound (TSL-9906 manufactured by Toshiba Silicone Co., Ltd.) and bisphenol A as a silicone-modified epoxy resin 1.8% by weight and 1,1,1, -tris (p-hydroxyphenyl) ethane (manufactured by Triquest Japan Co., Ltd., product number THPE-) previously vacuum-dried at 130 ° C. and 5 torr as a first curing agent for 3 hours. E, melting point 246 ° C.) 5.2% by weight, phenol novolac (manufactured by Sumitomo Durez Co., Ltd., product number PR) 51470, softening point 110 ° C.) 5.2% by weight, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., benzoic acid) 1.8% by weight as a flux compound, 2-phenyl-4-methylimidazole as a curing accelerator (Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.05 wt%, triphenylphosphine and 1,4-benzoquinone adduct 0.15 wt%, acrylonitrile butadiene rubber (Ube Industries, Ltd.) ), CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber (1.0% by weight) and silica (manufactured by Admatechs, SO-25H, average particle size 0.7 μm) 50.0% by weight as an inorganic filler. The resin composition for sealing was obtained by dispersing and kneading at room temperature with three rolls and performing defoaming treatment under vacuum.
The difference in melting point between the first curing agent and the second curing agent was 136 ° C.

(Example 6)
The same procedure as in Example 1 was performed except that the blending ratio of the first epoxy resin and the second epoxy resin was changed as follows.
Bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) 9.3 wt% as the first epoxy resin and diallyl bisphenol A type epoxy resin (Nipponization) as the second epoxy resin Made by Yakuhin Co., Ltd., RE-810NM, epoxy equivalent 210) 28.1 wt%.

(Example 7)
The same procedure as in Example 1 was performed except that the blending ratio of the first epoxy resin and the second epoxy resin was changed as follows.
Bisphenol F-type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin 33.7% by weight, diallyl bisphenol A-type epoxy resin (Nipponization) as the second epoxy resin Made by Yakuhin Co., Ltd., RE-810NM, epoxy equivalent 210) 3.7% by weight.

(Example 8)
The same procedure as in Example 1 was conducted except that the blending ratio of the epoxy resin was as follows.
Bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 11.2% by weight, diallyl bisphenol A type epoxy resin (Nipponization) as the second epoxy resin 9.4% by weight of RE-810NM, epoxy equivalent 210) manufactured by Yakuhin Co., Ltd., and 5: 1 reaction product of silicone compound (TSL-9906, manufactured by Toshiba Silicone Co., Ltd.) and bisphenol A as a silicone-modified epoxy resin The amount was 18.7% by weight.

Example 9
The procedure of Example 1 was repeated except that the content of the silicone-modified epoxy resin was reduced and the composition of the sealing resin composition was changed as follows.
Bisphenol F-type epoxy resin (Dainippon Ink and Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 28.9% by weight, diallyl bisphenol A-type epoxy resin (Nippon Kasei) as the second epoxy resin 9.7% by weight of RE-810NM, epoxy equivalent 210) manufactured by Yakuhin Co., Ltd., and 5: 1 reaction product of silicone compound (TSL-9906, manufactured by Toshiba Silicone Co., Ltd.) and bisphenol A as a silicone-modified epoxy resin 0.4% by weight of gentisic acid (manufactured by Midori Chemical Co., Ltd., gentisic acid “2,5-dihydroxybenzoic acid” previously dried in a vacuum at 130 ° C. and 5 torr as a first curing agent (first flux active curing agent) Acid ", melting point 202 [deg.] C.) 7.7% by weight, and in advance as a second curing agent (second flux active curing agent) Sebacic acid (Tokyo Chemical Industry Co., Ltd., sebacic acid, melting point 134 ° C.) 1.9% by weight vacuum-dried at 0 ° C. and 5 torr for 3 hours, and 2-phenyl-4-methylimidazole (Shikoku Chemicals) as a curing accelerator Industrial Co., Ltd. 2P4MZ 0.05% by weight, triphenylphosphine and 1,4-benzoquinone adduct 0.15% by weight, acrylonitrile butadiene rubber (Ube Industries, Ltd., CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber (1.2% by weight) and inorganic filler (silica (manufactured by Admatechs Co., Ltd., SO-25H, average particle diameter 0.7 μm) 50.0% by weight) Dispersion kneading was performed at room temperature with a roll, and defoaming treatment was performed under vacuum to obtain a sealing resin composition.

(Example 10)
The same procedure as in Example 1 was performed except that the content of the inorganic filler was changed and the composition of the sealing resin composition was changed as follows.
Bisphenol F type epoxy resin (Dainippon Ink Chemical Industries, Ltd., EXA-830LVP, epoxy equivalent 161) as the first epoxy resin 23.4% by weight and diallyl bisphenol A type epoxy resin (Nipponization) as the second epoxy resin 7.9% by weight of RE-810NM, epoxy equivalent 210) manufactured by Yakuhin Co., Ltd., and 5: 1 reaction product of silicone compound (TSL-9906, manufactured by Toshiba Silicone Co., Ltd.) and bisphenol A as a silicone-modified epoxy resin 1.6% by weight of gentisic acid (manufactured by Midori Chemical Co., Ltd., gentisic acid “2,5-dihydroxybenzoic acid” previously dried at 130 ° C. and 5 torr for 3 hours as a first curing agent (first flux active curing agent) Acid ”, melting point 202 ° C.) 6.2% by weight, and in advance as a second curing agent (second flux active curing agent) 1.6% by weight of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd., sebacic acid, melting point 134 ° C.) vacuum-dried at 0 ° C. and 5 torr for 3 hours, and 2-phenyl-4-methylimidazole (Shikoku Kasei) as a curing accelerator Industrial Co., Ltd. 2P4MZ 0.05% by weight, triphenylphosphine and 1,4-benzoquinone adduct 0.15% by weight, acrylonitrile butadiene rubber (Ube Industries, Ltd., CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber (0.9% by weight) and silica as an inorganic filler (manufactured by Admatechs Co., Ltd., SO-25H, average particle size 0.7 μm) were 58.2% by weight.

(Example 11)
The same procedure as in Example 1 was performed except that 50.0% by weight of silica having a different particle size (manufactured by Admatechs Co., Ltd., product number SE5101, average particle size 2 μm) was used as the inorganic filler.

(Comparative Example 1)
Example 2 was carried out in the same manner as in Example 1 except that the second epoxy resin was not used and the blending ratio of the epoxy resin was changed as follows.
Bisphenol F-type epoxy resin (Dainippon Ink Chemical Industries, Ltd., EXA-830LVP, epoxy equivalent 161) as the first epoxy resin, 37.4% by weight, and silicone compound as the silicone-modified epoxy resin (manufactured by Toshiba Silicone Co., Ltd.) , TSL-9906) and bisphenol A 5: 1 reaction product 1.9 wt%.

(Comparative Example 2)
The same procedure as in Example 1 was conducted, except that the sealing resin composition was blended as follows without using a silicone-modified epoxy resin.
29.2% by weight of bisphenol F type epoxy resin (Dainippon Ink & Chemicals, EXA-830LVP, epoxy equivalent 161) as the first epoxy resin and diallyl bisphenol A type epoxy resin (Nippon Kasei) as the second epoxy resin 9.7 parts by weight of RE-810NM, epoxy equivalent 210, manufactured by Yakuhin Co., Ltd., and gentisic acid (Midori Kagaku) previously vacuum-dried at 130 ° C. and 5 torr as a first curing agent (first flux active curing agent) for 3 hours 7.8% by weight of gentisic acid “2,5-dihydroxybenzoic acid”, melting point 202 ° C., manufactured by Co., Ltd., and vacuum at 80 ° C. and 5 torr for 3 hours in advance as a second curing agent (second flux active curing agent) 1.9% by weight of dried sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd., sebacic acid, melting point 134 ° C.) and 2-phenyl as a curing accelerator 4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., 2P4MZ) 0.05% by weight, adduct of triphenylphosphine and 1,4-benzoquinone 0.15% by weight, acrylonitrile butadiene rubber ( Ube Industries, Ltd., CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber (1.2% by weight) and silica as an inorganic filler (manufactured by Admatechs, SO-25H, average particle size 0.7 μm) 50.0 % By weight.

(Comparative Example 3)
The same procedure as in Example 1 was conducted, except that the sealing resin composition was blended as follows without using an inorganic filler.
Bisphenol F type epoxy resin (Dainippon Ink Chemical Co., Ltd., EXA-830LVP, epoxy equivalent 161) as the first epoxy resin is 56.1% by weight, diallyl bisphenol A type epoxy resin (Nippon Kay) as the second epoxy resin 18.7% by weight of RE-810NM, epoxy equivalent 210) manufactured by Yakuhin Co., Ltd., and 5: 1 reaction product of silicone compound (TSL-9906 manufactured by Toshiba Silicone Co., Ltd.) and bisphenol A as a silicone-modified epoxy resin 3.7% by weight, gentisic acid (manufactured by Midori Chemical Co., Ltd., gentisic acid “2,5-dihydroxybenzoic acid” previously vacuum-dried at 130 ° C. and 5 torr as a first curing agent (first flux active curing agent) Acid ”, melting point 202 ° C.) 15.0% by weight, and as a second curing agent (second flux active curing agent) In addition, sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd., sebacic acid, melting point 134 ° C.) 3.7% by weight dried at 80 ° C. and 5 torr for 3 hours and 2-phenyl-4-methylimidazole (Shikoku) as a curing accelerator Made by Kasei Kogyo Co., Ltd., 2P4MZ) 0.15% by weight, adduct of triphenylphosphine and 1,4-benzoquinone 0.35% by weight, acrylonitrile butadiene rubber (made by Ube Industries, Ltd.) as a stress reducing material CTBN1008SP, carboxyl group-terminated butadiene acrylic rubber) was 2.3% by weight.

The semiconductor device obtained in each example and comparative example was evaluated as follows. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Solder bump connectivity The continuity of 10 circuit boards to which solder bumps were connected by the above-mentioned method was checked using a hand probe type tester, and the ones with continuity were determined to be non-defective products (number of defective packages / total Number of packages).

2. Moisture absorption reflow test Solder bump connection was performed, 10 cured packages with 100% connection rate were selected, moisture absorbed at 30 ° C, 60%, 72 hours, then passed through reflow at a maximum temperature of 260 ° C three times, and sealing resin The appearance crack and the peeled state of the interface were examined by SAT. As for the peeling state of the interface, a package where peeling occurred even at one place was regarded as defective (number of peeling occurrence packages / total number of packages).

3. Temperature cycle (T / C) test Ten of the packages subjected to the moisture absorption reflow test that were not defective were subsequently subjected to a T / C test under the conditions of -55 ° C, 30 minutes / -125 ° C, 30 minutes. . The state of cracks and peeling was observed every 1000 cycles and a maximum of 1000 cycles. As for the peeling state of the interface, a package in which peeling occurred even at one place was regarded as defective (chip crack or number of peeling occurrence packages / total number of packages).

As is apparent from Table 1, in Examples 1 to 11, even when the resin composition containing the inorganic filler is used as a no-flow type underfill material, the connection between the semiconductor element and the substrate is caused by the weight of the semiconductor element. Became possible.
In Examples 1 to 3 and 6 to 11, no peeling occurred even after the moisture absorption treatment.
In Examples 1 to 3, 7 and 9 to 11, no peeling occurred even after the temperature cycle test.

  The resin composition of the present invention is mainly used for sealing a gap between a substrate and a semiconductor element having protruding electrodes.

FIG. 1 is a profile diagram showing a typical temperature profile for solder reflow. FIG. 2 is a schematic view schematically showing the manufacturing process of the semiconductor device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Board | substrate 11 Pad part 12 Syringe 2 Resin composition 2 'Sealing material 3 Semiconductor element 31 Solder bump 32 Flip chip bonder 4 Solder reflow furnace 10 Semiconductor device

Claims (13)

A resin composition used for sealing between a semiconductor element and a substrate,
A first epoxy resin that is liquid at room temperature;
A second epoxy resin having a higher curing start temperature than the liquid resin;
Silicone-modified epoxy resin,
And an inorganic filler.   The resin composition according to claim 1, wherein the second epoxy resin contains a diallyl bisphenol type epoxy resin.   The resin composition according to claim 2, wherein the diallyl bisphenol type epoxy resin is a diallyl bisphenol A type epoxy resin.   The resin composition according to any one of claims 1 to 3, further comprising a curing agent.   The resin composition according to claim 4, wherein the curing agent includes a first curing agent and a second curing agent having a melting point different from that of the first curing agent.   The resin composition according to claim 5, wherein a difference between the melting point of the first curing agent and the melting point of the second curing agent is 30 ° C. or more.   The resin composition according to claim 5 or 6, wherein at least one of the first curing agent and the second curing agent is a curing agent having flux activity.   The resin composition according to claim 7, wherein the curing agent having flux activity is a compound containing at least two phenolic hydroxyl groups in one molecule and a carboxyl group directly bonded to an aromatic group. The resin composition according to any one of claims 1 to 8, wherein the silicone-modified epoxy resin is represented by the following formula (1).

  The resin composition according to any one of claims 1 to 9, wherein the content of the inorganic filler is 80% by weight or less of the entire resin composition.   It is comprised with the resin composition in any one of Claim 1 thru | or 10, The sealing material characterized by the above-mentioned.   A semiconductor device, wherein a gap between the semiconductor element and the substrate is sealed with the sealing material according to claim 11. An application step of applying the resin composition according to any one of claims 1 to 10 to a portion on which a semiconductor element of the substrate is mounted;
A temporary pressure bonding step of mounting and pre-bonding a semiconductor element;
A method for manufacturing a semiconductor device, comprising: a curing step for curing the resin composition.

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