JP2010010368A - Semiconductor device, and manufacturing method of the same - Google Patents

Abstract

An object of the present invention is to provide a semiconductor device capable of suitably joining a semiconductor element having a through electrode and another semiconductor element.
A semiconductor device of the present invention includes a substrate, a first semiconductor element provided on at least one surface side of the substrate, and a second semiconductor element having a conductor portion penetrating in the thickness direction. In the semiconductor device, the first semiconductor element and the second semiconductor element are electrically connected via a projecting electrode, and the first semiconductor element and the second semiconductor element are interposed between the first semiconductor element and the second semiconductor element. And a first adhesive layer composed of a cured product of a resin composition containing a crosslinkable resin and a compound having flux activity.
[Selection] Figure 1

Description

  The present invention relates to a semiconductor device and a method for manufacturing the semiconductor device.

  In response to the recent increase in functionality of electronic devices and expansion to mobile applications, there is an increasing demand for higher density and higher integration of semiconductor devices, and IC packages are increasing in capacity and density. As a manufacturing method of these semiconductor devices, after sticking an adhesive sheet (dicing sheet) to a semiconductor wafer made of silicon, gallium, arsenic, etc., and cutting and separating (dividing into individual pieces) into individual semiconductor elements by dicing, Expanding and picking up individual semiconductor elements are performed, and then the semiconductor elements are transferred to an assembly process of a semiconductor device that is die-bonded to a metal lead frame, a tape substrate, an organic hard substrate, or the like.

On the other hand, there are remarkable technological innovations for reducing the size and weight of semiconductor devices, and various package structures have been proposed and commercialized. In recent years, an area mounting method in which a semiconductor element and a circuit board are bonded via a protruding electrode directly formed on a circuit surface of the semiconductor element is becoming mainstream instead of the conventional lead frame bonding. In addition, a method called a stacked package in which semiconductor elements are three-dimensionally stacked has become mainstream. When a plurality of semiconductor elements are arranged in a three-dimensional shape instead of a planar shape, the package can be made small. Furthermore, since the information exchanged between the semiconductor elements can be increased, the overall performance is improved.
As a technique for three-dimensionally laminating semiconductor elements, there is a technique called multi-chip package (MCP) in which semiconductor elements are connected by wire bonding. On the other hand, a through electrode (TSV: Through Silicon Via) opens a hole in a semiconductor element, fills the metal, and makes a connection between the semiconductor elements. This method eliminates the need for a connection wire, and can reduce the distance between semiconductor elements, and is expected to become mainstream in the future.

  In this through electrode, the gap between the semiconductor element and the circuit board is generally sealed with a resin composition for the purpose of reinforcing the joint portion and improving the reliability.

  As a resin sealing method, a capillary underfill method is generally used. This method is performed by applying a liquid sealing resin composition to one side or a plurality of surfaces of a semiconductor element and causing the resin composition to flow into the gap between the circuit board and the semiconductor element using a capillary phenomenon (see Patent Document 1). .

However, the cavity underfill method requires a process of bonding the semiconductor element and the through electrode using a flux and a flux cleaning process, so that the process becomes longer and environmental management such as cleaning waste liquid processing problems must be tightened. Don't be. Further, since the sealing is performed by a capillary phenomenon, the sealing time becomes long and there is a problem in productivity.
JP 2007-217708 A

An object of the present invention is to provide a semiconductor device capable of suitably bonding a semiconductor element having a through electrode and another semiconductor element.
Another object of the present invention is to provide a method for manufacturing a semiconductor device in which a semiconductor element having a through electrode and another semiconductor element are bonded with high productivity.

Such an object is achieved by the present invention described in the following (1) to (7).
(1) A semiconductor device comprising a substrate, a first semiconductor element provided on at least one surface side of the substrate, and a second semiconductor element having a conductor portion penetrating in the thickness direction, One semiconductor element and the second semiconductor element are electrically connected via a protruding electrode, and a resin and flux capable of crosslinking reaction are provided between the first semiconductor element and the second semiconductor element. A semiconductor device comprising a first adhesive layer made of a cured product of a resin composition containing an active compound.
(2) The substrate and the first semiconductor element are electrically connected via a protruding electrode, and a resin capable of crosslinking reaction and a flux are provided between the substrate and the first semiconductor element. The semiconductor device according to (1) above, wherein a second adhesive layer composed of a cured product of a resin composition containing an active compound is disposed.
(3) The semiconductor device according to (1) or (2), wherein the resin composition further includes a film-forming resin.
(4) The semiconductor device according to any one of (1) to (3), wherein the compound having the flux activity is a compound having at least one of a carboxyl group and a phenolic hydroxyl group.
(5) The semiconductor device according to any one of (1) to (4), wherein the compound having the flux activity is capable of acting as a curing agent for the resin capable of crosslinking reaction.
(6) A layer composed of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity and a dicing sheet layer are arranged on one surface of a semiconductor wafer having a plurality of conductor portions penetrating in the thickness direction. A step of obtaining a second semiconductor element having a conductor portion penetrating in a thickness direction by dividing the wafer for semiconductor, a compound capable of cross-linking the second semiconductor element, and a compound having a flux activity A step of picking up from a dicing sheet layer in a state having a layer composed of a resin composition containing the second semiconductor element, and the other of the first semiconductor elements mounted on one surface side of the substrate And a step of mounting on the surface side of the semiconductor device.
(7) The first semiconductor element and the substrate are joined in advance with a second adhesive layer made of a cured product of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity. The method for manufacturing a semiconductor device according to (6) above.

According to the present invention, a semiconductor device capable of suitably bonding a semiconductor element having a through electrode and another semiconductor element can be obtained.
In addition, according to the present invention, it is possible to obtain a method of manufacturing a semiconductor device in which a semiconductor element having a through electrode and another semiconductor element are bonded with high productivity.

The semiconductor device and the manufacturing method thereof according to the present invention will be described below.
A semiconductor device of the present invention is a semiconductor device having a substrate, a first semiconductor element provided on at least one surface side of the substrate, and a second semiconductor element having a conductor portion penetrating in the thickness direction. The first semiconductor element and the second semiconductor element are electrically connected via a protruding electrode, and a bridging reaction is possible between the first semiconductor element and the second semiconductor element. A first adhesive layer composed of a cured product of a resin composition containing an active resin and a compound having flux activity is disposed.
Also, the method for manufacturing a semiconductor device of the present invention comprises a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity on one surface of a semiconductor wafer having a plurality of conductor portions penetrating in the thickness direction. Disposing the layer to be processed and the dicing sheet layer, separating the semiconductor wafer into pieces, obtaining a second semiconductor element having a conductor portion penetrating in the thickness direction, and cross-linking the second semiconductor element A step of picking up from a dicing sheet layer in a state having a layer composed of a resin composition including a resin having a possible resin and a flux activity, and the second semiconductor element picked up on one surface side of the substrate And mounting on the other surface side of the mounted first semiconductor element.

First, a semiconductor device will be described in detail based on a preferred embodiment shown in FIG.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention.
As shown in FIG. 1, a semiconductor device 100 includes a substrate 10, a first semiconductor element 1 mounted on the upper side of the substrate 10 (upper side in FIG. 1), and an upper side of the first semiconductor element (in FIG. 1). And a second semiconductor element 2 mounted on the upper side.
On the upper surface of the substrate 10, a circuit pattern (not shown) is formed, and electrode pads are arranged.
The first semiconductor element 1 and the substrate 10 are electrically connected via solder bumps 11. Between the 1st semiconductor element 1 and the board | substrate 10, it is the 2nd comprised by the hardened | cured material of the resin composition containing the resin which can carry out a crosslinking reaction, and the compound which has a flux activity so that the circumference | surroundings of the solder bump 11 may be protected. An adhesive layer 12 is disposed.

  The first semiconductor element 1 is formed with a conductor portion 13 penetrating in the thickness direction, and an electric signal can be exchanged between the functional surface 14 and the back surface of the first semiconductor element 1. It has become. Thereby, it is not necessary to use a bonding wire, and the semiconductor device can be thinned. Furthermore, since the transmission distance of the electric signal can be shortened compared with the case where the bonding wire is used, the response speed can be improved.

  The first semiconductor element 1 and the second semiconductor element 2 are also electrically connected via the solder bump 21. Between the 1st semiconductor element 1 and the 2nd semiconductor element 2, it is comprised with the hardened | cured material of the resin composition containing the resin which can carry out a crosslinking reaction, and the compound which has a flux activity so that the circumference | surroundings of the solder bump 21 may be protected. A first adhesive layer 22 is disposed.

  The second semiconductor element 2 is formed with a conductor portion 23 penetrating in the thickness direction, and an electric signal can be exchanged between the functional surface 24 and the back surface of the second semiconductor element 2. ing. Thereby, it is not necessary to use a bonding wire, and the semiconductor device can be thinned. Furthermore, since the transmission distance of the electric signal can be shortened compared with the case where the bonding wire is used, the response speed can be improved.

Each configuration will be described below.
As the substrate 10, for example, a ceramic substrate or an organic substrate can be used. As the ceramic substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. As the organic substrate, a polyimide film substrate using a polyimide film as a substrate, an FR-4 substrate in which a glass cloth is impregnated with an epoxy resin, a BT substrate in which a bismaleimide-triazine resin is impregnated, or the like can be used.

  As the first semiconductor element, for example, a memory, a logic, a processor, or the like is used, and a size of about 1 to 20 mm square can be suitably used.

  The size of the solder bump 11 connecting the first semiconductor element and the substrate 10 is not particularly limited, but is preferably 10 to 600 μm, particularly preferably 30 to 200 μm.

  Moreover, as a resin composition of the 2nd contact bonding layer 12 comprised by the hardened | cured material of the resin composition containing the resin which can perform the crosslinking reaction which protects the circumference | surroundings of the solder bump 11, and the compound which has flux activity, the following is mentioned, for example Can be mentioned.

Further, as the second adhesive layer 12 that protects the periphery of the solder bump 11, a so-called underfill material can be used. For example, epoxy resins, polyamide resins, polyimide resins, maleimide resins, fluorine resins, silicone resins, etc., mixed with one or more types, curing agents, inorganic fillers, various coupling agents, etc. A liquid underfill material can be obtained by addition.
The underfill material is applied to one side or a plurality of surfaces of the semiconductor element, and the resin composition is poured into the gap between the circuit board and the semiconductor element using a capillary phenomenon to be cured, thereby forming a cured resin and protecting the electrode.

  In addition, although the case where what was called an underfill material was used as the 2nd contact bonding layer 12 was demonstrated, it is not limited to this, Curing | curing of the resin composition containing the compound which has crosslinkable reaction and a flux activity which are mentioned later You may use what is comprised with a thing.

  As the second semiconductor element 2, for example, a memory, a logic, a processor, or the like is used, and a size approximately the same as that of the first semiconductor element and about 1 to 20 mm square can be preferably used.

  The size of the solder bump 21 connecting the second semiconductor element 2 and the first semiconductor element 1 is not particularly limited, but is preferably 10 to 300 μm, and particularly preferably 20 to 100 μm.

Moreover, as a resin composition of the 1st contact bonding layer 22 comprised with the hardened | cured material of the resin composition containing the resin which can perform the crosslinking reaction which protects the circumference | surroundings of the solder bump 21, and the compound which has flux activity, the following is mentioned, for example Can be mentioned.
Examples of the resin capable of crosslinking reaction include those classified into so-called thermosetting resins such as epoxy resins, oxetane resins, phenol resins, (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, and maleimide resins. Further, a thermoplastic resin having a functional group such as a carboxyl group or an epoxy group can also be exemplified as the resin capable of crosslinking reaction of the present invention. Among these, an epoxy resin excellent in curability and storage stability, heat resistance, moisture resistance, and chemical resistance of a cured product is preferably used.

  As the epoxy resin, either an epoxy resin that is solid at room temperature or an epoxy resin that is liquid at room temperature may be used. Further, an epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature may be used in combination. Thereby, the design freedom of the melting behavior of the first adhesive layer 22 can be further increased.

  The epoxy resin that is solid at room temperature is not particularly limited, and is a novolak such as a bisphenol A type epoxy resin, a bisphenol type epoxy resin such as a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. Type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, trifunctional epoxy resin, and polyfunctional epoxy resin such as tetrafunctional epoxy resin. More specifically, the epoxy resin that is solid at room temperature preferably includes a trifunctional epoxy resin and a cresol novolac epoxy resin that are solid at room temperature. Thereby, the moisture resistance reliability of the semiconductor device 100 can be improved.

  The epoxy resin that is liquid at room temperature is not particularly limited, and is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A nuclear hydrogenated type epoxy resin, 4-t-butylcatechol type epoxy resin, naphthalene. Type epoxy resin and the like.

  The content of the resin capable of crosslinking reaction is preferably 25% by weight or more and 75% by weight or less, and particularly preferably 45% by weight or more and 70% by weight or less, based on the entire resin composition. When the content is within the above range, good curability can be obtained, and good melting behavior can be designed.

The compound having the flux activity is not particularly limited as long as it has an effect of removing the metal oxide film by heating or the like. For example, an organic acid such as an active rosin or an organic compound having a carboxy group, an amine, a phenol, an alcohol, an azine, or the like may have a flux activity by itself or promote a flux activity.
More specifically, the compound having the flux activity includes a compound having at least one carboxyl group and / or phenolic hydroxyl group in the molecule, which may be liquid or solid.

  Examples of the compound containing a carboxyl group include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, aliphatic carboxylic acids, and aromatic carboxylic acids. Examples of the flux compound having a phenolic hydroxyl group include phenols.

  Examples of the aliphatic acid anhydride include succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, and the like.

  Examples of the alicyclic acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid. An acid anhydride etc. are mentioned.

  Examples of the aromatic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, glycerol tris trimellitate, and the like.

  Examples of the aliphatic carboxylic acid include compounds represented by the following formula (1).

  In the compound represented by the formula (1), n in the formula (1) is 3 or more from the balance of the flux activity, the outgas at the time of adhesion, the elastic modulus after curing of the first adhesive layer 22 and the glass transition temperature. It is preferably 10 or less, particularly preferably 4 or more and 8 or less. By setting n to be equal to or more than the lower limit value, an increase in the elastic modulus after curing can be suppressed, and the adhesiveness to the adherend can be improved. Moreover, by making n below the upper limit, it is possible to suppress a decrease in elastic modulus and further improve connection reliability.

Examples of the compound represented by the formula (1) include n = 3 glutaric acid (HOOC— (CH ₂ ) ₃ —COOH), n = 4 adipic acid (HOOC— (CH ₂ ) ₄ —COOH), n = 5 pimelic acid (HOOC— (CH ₂ ) ₅ —COOH), n = 8 sebacic acid (HOOC— (CH ₂ ) ₈ —COOH), n = ₁₀ HOOC— (CH ₂ ) ₁₀ —COOH— and the like Can be mentioned.
Other aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid pivalate, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, Examples include oleic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, and oxalic acid.

  Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, platnic acid, pyromellitic acid, merit acid, triyl acid, and xylyl acid. , Hemelitic acid, mesitylene acid, prenylic acid, toluic acid, cinnamic acid, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6 -Dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid (3,4,5-trihydroxybenzoic acid), 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as phenolphthalin; diphenolic acid and the like.

  Examples of the compound having a phenolic hydroxyl group include phenol, o-cresol, 2,6-xylenol, p-cresol, m-cresol, o-ethylphenol, 2,4-xylenol, 2,5 xylenol, and m-ethyl. Phenol, 2,3-xylenol, meditol, 3,5-xylenol, p-tertiarybutylphenol, catechol, p-tertiaryamylphenol, resorcinol, p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, bisphenol AF , Monomers containing phenolic hydroxyl groups such as biphenol, diallyl bisphenol F, diallyl bisphenol A, trisphenol, tetrakisphenol, phenol novolac resin, o-cresol novola Click resin, bisphenol F novolac resin, bisphenol A novolac resins.

Moreover, it is preferable that the compound which has such flux activity is a hardening | curing agent which has the flux activity which is taken in three-dimensionally by reaction with resin which can be cross-linked like an epoxy resin. Thereby, in addition to omitting the cleaning step after the flux activation, the reliability can be further improved.
As the curing agent having this flux activity, for example, at least two phenolic hydroxyl groups that can be added to a resin capable of crosslinking reaction such as an epoxy resin in one molecule, and a flux action on a metal oxide film, Examples thereof include compounds having at least one carboxyl group directly bonded to an aromatic group in one molecule. Specifically, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid Benzoic acid derivatives such as acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as acids; phenolphthaline; and diphenolic acid.
These compounds having flux activity may be used alone or in combination of two or more.

  The content of the compound having the flux activity is not particularly limited, but is preferably 1% by weight or more and 30% by weight or less of the entire resin composition, and particularly 5% by weight or more and 25% by weight or less. Is preferred. If the content is less than the lower limit, the effect of flux activity may be insufficient, and if the content exceeds the upper limit, a resin capable of crosslinking reaction and a compound having unreacted flux activity may remain, May cause migration. Further, when the content is within the above range, the oxide film on the surface of the copper foil is reduced, and a good bond having high strength can be obtained.

The resin composition is not particularly limited, but may contain a curing agent.
Examples of the curing agent include phenols, amines, and thiols. When an epoxy resin is used as a resin capable of crosslinking reaction, good reactivity with the epoxy resin, low dimensional change upon curing, and appropriate physical properties after curing (for example, heat resistance, moisture resistance, etc.) are obtained. In this respect, phenols are preferably used.

  Although it does not specifically limit as said phenols, When the physical property after hardening of the 2nd adhesive agent 2 is considered, bifunctional or more is preferable. Examples include bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, trisphenol, tetrakisphenol, phenol novolacs, cresol novolacs, etc., but melt viscosity, reaction with epoxy resin When considering the properties and physical properties after curing, phenol novolacs and cresol novolacs can be preferably used.

  When phenol novolacs are used as the curing agent, the content is not particularly limited, but from the viewpoint of surely curing the crosslinkable resin, it is preferably 5% by weight or more of the total resin composition, 10 weight% or more is preferable. Moreover, if epoxy resin and unreacted phenol novolak remain, it causes migration. Therefore, in order not to remain as a residue, the content is preferably 30% by weight or less, and particularly preferably 25% by weight or less, based on the entire resin composition.

  When the resin capable of crosslinking reaction is an epoxy resin, the content of the phenol novolac resin may be defined by an equivalent ratio with respect to the epoxy resin. Specifically, the equivalent ratio of phenol novolac to epoxy resin is preferably 0.5 or more and 1.2 or less, particularly preferably 0.6 or more and 1.1 or less, and most preferably 0.7 or more and 0.98 or less. Is preferred. By setting the equivalent ratio of the phenol novolac resin to the epoxy resin to be equal to or higher than the lower limit value, heat resistance and moisture resistance after curing can be ensured, and by setting the equivalent ratio to be equal to or lower than the upper limit value, The amount of the epoxy resin and the unreacted residual phenol novolac resin can be reduced, and the migration resistance is improved.

Examples of other curing agents include imidazole compounds and phosphorus compounds.
Although it does not specifically limit as said imidazole compound, It is preferable to use the imidazole compound whose melting | fusing point is 150 degreeC or more. Thereby, it becomes easy to aim at coexistence with hardening of the 1st adhesion layer 22, and a flux function. That is, if the melting point of the imidazole compound is too low, the oxide film of the solder bump is removed, the adhesive tape is cured before the solder bump and the electrode are metal-bonded, the connection becomes unstable, and the adhesive tape is stored. It is possible to suppress the case where the property is lowered.
Examples of the imidazole compound having a melting point of 150 ° C. or higher include 2-phenylhydroxyimidazole, 2-phenyl-4-methylhydroxyimidazole, 2-phenyl-4-methylimidazole, and the like. In addition, there is no restriction | limiting in particular in the upper limit of melting | fusing point of an imidazole compound, For example, according to the adhesion temperature of the 1st contact bonding layer 22, it can set suitably.

  When an imidazole compound is used as the curing agent, the content is not particularly limited, but is preferably 0.005% by weight or more and 10% by weight or less of the entire resin composition, particularly 0.01% by weight or more, 5% by weight or less is preferable. By making content of an imidazole compound more than the said lower limit, the function as a curing catalyst of resin which can carry out a crosslinking reaction can be exhibited more effectively, and the sclerosis | hardenability of the 1st contact bonding layer 22 can be improved. Moreover, by setting the blending ratio of the imidazole compound to the upper limit value or less, the melt viscosity of the resin is not too high at the temperature at which the solder melts, and a good solder joint structure is obtained. In addition, the storage stability of the first adhesive layer 22 can be further improved.

  Examples of the phosphorus compound include triphenylphosphine; a molecular compound of a tetra-substituted phosphonium and a polyfunctional phenol compound; a molecular compound of a tetra-substituted phosphonium, a proton donor, and a trialkoxysilane compound. Among these, a molecular compound of a tetra-substituted phosphonium and a polyfunctional phenol compound, which is excellent in the fast curing property of the second adhesive 2, the corrosiveness to the aluminum pad of the semiconductor element, and the storability of the first adhesive layer 22. And a molecular compound of a tetra-substituted phosphonium, a proton donor, and a trialkoxysilane compound is particularly preferable.

The resin composition is not particularly limited, but may include a film-forming resin different from the resin capable of crosslinking reaction.
Examples of the film-forming resin include phenoxy resin, polyester resin, polyurethane resin, polyimide resin, siloxane-modified polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, Polyacetal resin, polyvinyl butyral resin, polyvinyl acetal resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl acetate, nylon Acrylic rubber or the like can be used. These may be used alone or in combination of two or more.

  When a phenoxy resin is used as the film-forming resin, a phenoxy resin having a number average molecular weight of 5,000 to 15,000 is preferable. By using such a phenoxy resin, the fluidity of the adhesive tape before curing can be suppressed, and the interlayer thickness can be made uniform. Examples of the skeleton of the phenoxy resin include, but are not limited to, bisphenol A type, bisphenol F type, and biphenyl skeleton type. Preferably, a phenoxy resin having a saturated water absorption rate of 1% or less is preferable because foaming, peeling, and the like can be suppressed even at high temperatures during bonding and solder mounting.

In addition, as the film-forming resin, a resin having a nitrile group, an epoxy group, a hydroxyl group, or a carboxyl group may be used for the purpose of improving adhesiveness or compatibility with other resins. For example, acrylic rubber can be used.
When acrylic rubber is used as the film-forming resin, it is possible to improve the film formation stability when producing a film-like adhesive tape. In addition, since the elastic modulus of the adhesive tape can be reduced and the residual stress between the adherend and the adhesive tape can be reduced, the adhesion to the adherend can be improved.

  The acrylic rubber is preferably a (meth) acrylic acid ester copolymer containing a monomer unit having an epoxy group, a hydroxyl group, a carboxyl group, a nitrile group or the like. Thereby, the adhesiveness to adherends, such as the back surface of a semiconductor element, and the coating material on a semiconductor element, can be improved more. Examples of monomers used in such a (meth) acrylic acid ester copolymer include glycidyl (meth) acrylate having a glycidyl group, (meth) acrylate having a hydroxyl group, (meth) acrylate having a carboxyl group, and a nitrile group. Examples include (meth) acrylonitrile.

  Among these, it is particularly preferable to use a (meth) acrylic acid ester copolymer containing a monomer unit having a glycidyl group or a carboxyl group. Thereby, hardening of a resin composition is further accelerated | stimulated and also the adhesiveness with respect to a to-be-adhered body can be improved.

  In the case of using a (meth) acrylic acid ester copolymer containing a monomer unit having a carboxyl group, the content of the monomer unit having a carboxyl group in the copolymer is further improved in terms of improving the adhesion to the adherend. For example, it is 0.5% by weight or more, preferably 1% by weight or more of the entire (meth) acrylic acid ester copolymer. In addition, the content of the monomer unit having a carboxyl group is, for example, 10% by weight or less, preferably 5% by weight or less of the entire (meth) acrylic acid ester copolymer, from the viewpoint of further improving the storage stability of the adhesive film. is there.

  The weight average molecular weight of the (meth) acrylic acid ester copolymer is, for example, 1,000 or more and 1,000,000 or less, and preferably 3,000 or more and 900,000 or less. By setting it as the said range, the film formability of a resin composition can further be improved and the fluidity | liquidity at the time of adhesion | attachment can be ensured.

  The weight average molecular weight of the (meth) acrylic acid ester copolymer can be measured, for example, by gel permeation chromatography (GPC). Examples of measurement conditions include a high-speed GPC SC-8020 device manufactured by Tosoh Corporation. In the column, TSK-GEL GMHXL-L, temperature 40 ° C., and solvent tetrahydrofuran can be used.

  The glass transition temperature of the (meth) acrylic acid ester copolymer is, for example, 0 ° C. or higher, preferably 5 ° C. or higher from the viewpoint of further improving workability by suppressing the adhesion of the second adhesive layer 22 from becoming too strong. It is. Further, the glass transition temperature of the (meth) acrylic acid ester copolymer is, for example, 30 ° C. or less, preferably 20 ° C. or less, from the viewpoint of further improving the adhesiveness at a low temperature.

  The glass transition temperature of the (meth) acrylic acid ester copolymer is increased from −65 ° C. at a constant load (10 mN) using, for example, a thermomechanical property analyzer (manufactured by Seiko Instruments Inc., TMA / SS6100). It can be measured from the inflection point when pulled while increasing the temperature at a temperature rate of 5 ° C./min.

  Although content of film forming resin is not specifically limited, It is preferable to set it as 5 to 50 weight% of the whole said resin composition. When the film-forming resin is blended within the above range, the decrease in film formability is suppressed and the increase in the elastic modulus after the first adhesive layer 22 is cured is suppressed. Adhesion can be further improved. Moreover, the increase in the melt viscosity of the 1st contact bonding layer 22 is suppressed by setting it as the said range.

  In addition, when properties such as heat resistance, dimensional stability and moisture resistance are particularly required, it is preferable to further contain an inorganic filler. Examples of such inorganic fillers include silicates such as talc, fired clay, unfired clay, mica, and glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), and powders such as crystalline silica. 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, silica powders such as fused silica and crystalline silica are preferable, and spherical fused silica is particularly preferable.

  By including an inorganic filler in the resin composition, the heat resistance, moisture resistance, strength and the like after the resin composition is cured can be improved, and the peelability of the first adhesive layer 22 from the protective film is improved. Can be made. Although the shape of the inorganic filler is not particularly limited, it is preferably a true sphere, whereby a resin composition suitable for the first adhesive layer 22 having no particular anisotropy can be provided.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 0.5 μm or less, particularly preferably 0.01 to 0.5 μm, and most preferably 0.01 to 0.3 μm. If the average particle size is too small, the inorganic filler tends to aggregate, resulting in a decrease in strength. On the other hand, if the average particle size is too large, the transparency of the first adhesive layer 22 is decreased, and the position on the surface of the semiconductor element is reduced. It may be difficult to recognize the alignment mark, and it may be difficult to align the semiconductor element and the substrate.

  Here, although content of an inorganic filler is not specifically limited, 10 to 60 weight% of the whole said resin composition is preferable, and 20 to 50 weight% is especially preferable. If the content of the inorganic filler is too small, the effect of improving heat resistance, moisture resistance, strength and the like may be reduced. On the other hand, if the content is too large, the transparency may be lowered or the first adhesive layer 22 may be tacked. May decrease.

  The resin composition may further include a silane coupling agent. By setting it as the structure containing a silane coupling agent, the adhesiveness to the to-be-adhered thing of the 1st contact bonding layer 22 can further be improved. Examples of the silane coupling agent include an epoxy silane coupling agent and an aromatic-containing aminosilane coupling agent. These may be used alone or in combination of two or more. Although content of a silane coupling agent is not specifically limited, It is preferable to set it as 0.01 to 5 weight% of the said whole resin composition.

The resin composition may contain components other than those described above. For example, various additives may be appropriately added in order to improve various properties such as resin compatibility, stability, and workability.
・

  The first adhesive layer 22 is composed of a cured product of the resin composition as described above. Thereby, an electrode can be protected and connection reliability can be improved.

Next, a method for manufacturing a semiconductor device will be described.
FIG. 2 is a schematic view showing an example of a method for manufacturing a semiconductor device of the present invention.
First, a laminate composed of a layer composed of a resin composition containing a crosslinkable resin and a compound having flux activity and a dicing sheet layer are produced.
As shown in FIG. 2 (a), a resin composition containing a compound capable of crosslinking reaction and a compound having flux activity is applied to the support substrate 5 and dried to obtain a resin layer 12 '. Next, the laminate 7 is obtained by laminating with a laminator or the like so that the resin layer 12 ′ and the adhesive layer 6 of the dicing sheet layer composed of the support base material 51 and the adhesive layer 6 are adjacent to each other (FIG. 2). (B)).
The support base material 5 is peeled from the laminate 7 to form a resin layer 12 ′ and one surface (the upper surface in FIG. 2) of the semiconductor wafer 8 having a plurality of conductor portions 81 penetrating in the thickness direction. Then, they are stacked so as to be adjacent to each other (FIG. 2C).
Here, the supporting substrate 51 is not particularly limited, and resin films such as polyester, polyethylene, polypropylene, polybutene, polybutadiene, vinyl chloride, ethylene-methacrylic acid copolymer, and crosslinked films of these resins, and further these The film which apply | coated silicone resin etc. to the resin surface and peel-processed can be mentioned.

  Next, it installs in a dicer table so that the support base material 51 of this laminated body 7 may contact | connect the upper surface of a dicer table (not shown). Next, a wafer ring is installed around the semiconductor wafer 8 to fix the semiconductor wafer 8. Then, the semiconductor wafer 8 is cut with a blade to divide the semiconductor wafer 8 into individual pieces, thereby obtaining a semiconductor element having a resin layer 12 'and a conductor portion penetrating in the thickness direction.

Next, the support base 51 is stretched with an expanding device, the semiconductor elements having the resin layer 12 ′ separated into pieces are opened at regular intervals, and then picked up, the substrate on which the semiconductor elements are mounted, It is mounted on the semiconductor element. Then, the resin layer 12 ′ is heated and cured to obtain a semiconductor device in which two semiconductor elements are stacked as an adhesive layer.
In the present invention, since the resin layer 12 ′ having the flux activity as described above is used, the flux treatment is not required when soldering the semiconductor elements. It also has excellent reflow resistance.

  In the above-described embodiment, two semiconductor elements are stacked. However, a plurality of three or four semiconductor elements may be stacked.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example 1
1. Production of resin layer Epoxy resin (NC6000 (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.)) 47.00% by weight as a resin capable of crosslinking reaction, and acrylate copolymer (butyl acrylate) as a film-forming resin -Ethyl acrylate-Acrylonitrile-Acrylic acid-Hydroxyethyl acrylate copolymer, manufactured by Nagase ChemteX Corporation, SG-708-6, weight average molecular weight: 500,000) 19.51% by weight and acrylic resin (acrylic Acid-styrene copolymer, weight average molecular weight: 5,500, UC-3900, manufactured by Toa Gosei Co., Ltd.) 9.75% by weight, solid phenol resin (PR-53647, hydroxyl group equivalent 104 g / OH group) as a curing agent, Sumitomo Bakelite Co., Ltd.) 10.26% by weight, imidazole compound (2P4M) as curing accelerator HZ, manufactured by Shikoku Chemicals Co., Ltd.) 0.08% by weight, phenolphthaline 12.88% by weight as a flux compound, propyltrimethoxysilane (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.52 as a coupling agent % By weight was dissolved in methyl ethyl ketone (MEK) to obtain a resin varnish having a resin solid content of 40%.
The above resin varnish was applied to a polyethylene terephthalate film (thickness: 38 μm) as a release film using a comma coater, and then dried at 90 ° C. for 5 minutes to obtain a resin layer having a thickness of 35 μm.

2. Production of Dicing Sheet Layer Cleartech CT-H717 (manufactured by Kuraray Co., Ltd.) was formed into a film having a thickness of 100 μm with an extruder, and the surface was subjected to corona treatment to obtain a base film.
Next, a weight average molecular weight of 500,000 obtained by copolymerizing 50 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of butyl acrylate, 37 parts by weight of vinyl acetate, and 3 parts by weight of 2-hydroxyethyl methacrylate. The copolymer was peeled and applied to a 38 μm thick polyester film (corresponding to the cover film of the adhesive layer) so that the thickness after drying was 10 μm, and dried at 80 ° C. for 5 minutes. Obtained. Then, this adhesive layer was laminated on the corona-treated surface of the substrate film described above to obtain a substrate film and an adhesive layer (dicing sheet layer).

(3) Manufacture of laminated body Only the resin layer of the resin layer with a release film (leave only the part bonded to the wafer) is half-cut, the cover film is peeled off from the dicing sheet layer, and the resin layer is bonded. Pasted and laminated. Thereby, the laminated body by which a base film, an adhesive layer, a resin layer, and a cover film were comprised in this order was obtained.

(4) Production of Second Semiconductor Element The cover film of this laminate is peeled off, and the resin layer surface is attached to the back surface of the semiconductor wafer (8 inches, 100 μm) at a temperature of 110 ° C. and a pressure of 0.3 MPa. A semiconductor wafer having Next, this semiconductor wafer was converted into a 7 mm × 7 mm square semiconductor element (number of electrodes 480, post diameter 30 μm, height 20 μm, pitch 50 μm, using a dicing saw at a spindle rotation speed of 30,000 rpm and a cutting speed of 50 mm / sec. Dicing (cutting) into a size of a tin silver solder height of 10 μm was performed. And it pushed up from the back surface of the resin layer, it peeled between the adhesion layer and resin layer of a dicing sheet, and the 2nd semiconductor element which the resin layer adhered was obtained.

3. Manufacturing of semiconductor device In advance, the first semiconductor element (size 7 mm × 7 mm, thickness 100 μm, number of electrodes 480, post diameter 30 μm, height 20 μm, pitch 50 μm, tin silver solder height 10 μm) is a solder resist (Taiyo Ink Manufacturing Co., Ltd.) Manufactured by: PSR4000 AUS308) coated BT (bismaleimide-triazine) resin substrate (0.8 mmt) bonded to the second semiconductor element having the above resin layer, the resin layer, and the first semiconductor After positioning using a flip chip bonder so that the element is adjacent, it was pressure-bonded and mounted at 250 ° C. for 10 seconds. Then, the resin layer was cured by heating at 180 ° C. for 60 minutes to obtain an adhesive layer, and a semiconductor device in which two semiconductor elements were stacked was obtained.

(Example 2)
The resin layer was the same as Example 1 except that the following was used.
An acrylic ester copolymer (acrylic acid) was used without using an acrylic resin (acrylic acid-styrene copolymer, weight average molecular weight: 5,500, UC-3900, manufactured by Toa Gosei Co., Ltd.) as a film-forming resin. Butyl-ethyl acrylate-acrylonitrile-acrylic acid-hydroxyethyl acrylate copolymer, manufactured by Nagase ChemteX Corporation, SG-708-6, weight average molecular weight: 500,000) was 29.26% by weight.

(Example 3)
The resin layer was the same as Example 1 except that the following was used.
A resin capable of crosslinking reaction was prepared by using an epoxy resin (NC6000 (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd.)) 37.60% by weight, and an acrylate copolymer (butyl acrylate-acrylic acid) as a film-forming resin. Ethyl-acrylonitrile-acrylic acid-hydroxyethyl acrylate copolymer, manufactured by Nagase ChemteX Corporation, SG-708-6, weight average molecular weight: 500,000) 15.60% by weight and acrylic resin (acrylic acid-styrene) Copolymer, weight average molecular weight: 5,500, UC-3900, manufactured by Toagosei Co., Ltd.) 7.80% by weight, solid phenol resin (PR-53647, hydroxyl group equivalent 104 g / OH group, Sumitomo Bakelite (as a curing agent) 8) 21% by weight, imidazole compound (2P4MHZ, Shikoku Chemicals) as a curing accelerator Co., Ltd.) 0.07% by weight, phenolphthaline 10.3% by weight as a flux compound, and propyltrimethoxysilane (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.42% by weight as methyl ethyl ketone ( In MEK), silica (Quatron SP-03B Fuso Chemical Industry Co., Ltd., average particle size 0.02 um silica) was further added and dispersed.

Example 4
The resin layer was the same as Example 1 except that the following was used.
A resin capable of crosslinking reaction was prepared by using an epoxy resin (epoxy equivalent 180 g / eq, Epicron 840S, Dainippon Ink & Chemicals, Inc.) 62.5% by weight, and a phenoxy resin (YL-6854, Japan Epoxy Resin ( Co., Ltd.) 25.00% by weight, solid phenol resin (PR-53647, hydroxyl group equivalent 104 g / OH group, manufactured by Sumitomo Bakelite Co., Ltd.) 31.30% by weight as a curing agent, phosphorus compound (tetra Phenylphosphine / phenyltrimethoxysilane / 2,3-dihydroxynaphthalene molecular compound) 0.50% by weight, 5.70% by weight of sebacic acid as a flux compound dissolved in methyl ethyl ketone (MEK), and a resin with a solid content of 40% A varnish was obtained.

(Comparative Example 1)
The semiconductor wafer was diced (cut) into a size of 7 mm × 7 mm square semiconductor element using a dicing saw at a spindle rotation speed of 30,000 rpm and a cutting speed of 50 mm / sec to obtain a first semiconductor element. Next, a BT (bismaleimide-triazine) resin substrate (0.8 mmt) coated with a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd .: PSR4000 AUS308) is applied to the back surface (opposite surface of the functional device surface) of the semiconductor element. ) And a flip chip bonder, and then subjected to pressure bonding at 250 ° C. for 10 seconds to obtain a flip chip package. Next, excess flux was cleaned using a flux cleaning solution. Thereafter, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., product number CRP-4152D1) was poured between the semiconductor element and the substrate and cured at 150 ° C. for 2 hours to obtain a semiconductor device. Next, another semiconductor wafer was measured using a dicing saw with a spindle rotation speed of 30,000 rpm, a cutting speed of 50 mm / sec, and a 5 mm × 5 mm square semiconductor element (number of electrodes 480, post diameter 30 μm, height 20 μm, pitch 50 μm). The second semiconductor element was obtained by dicing (cutting) into a size of tin silver solder height of 10 μm. A flux is applied to the back surface (opposite surface of the functional device surface) of the second semiconductor element, alignment is performed on the first semiconductor element using a flip chip bonder, and then crimped at 250 ° C. for 10 seconds to form a flip chip package. Got. Next, excess flux was cleaned using a flux cleaning solution. Thereafter, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., product number CRP-4120B2) was poured between the first semiconductor element and the second semiconductor element, and cured at 150 ° C. for 2 hours to obtain a semiconductor device. .

  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. Connection reliability Connection reliability was evaluated based on whether or not the obtained semiconductor device was conductive after the heat cycle test.
Specifically, the connection resistance between the semiconductor element and the substrate was measured with a digital multi-digital multimeter. The measurement was performed both after manufacturing the semiconductor device and after 1,000 cycles of a temperature cycle of -65 ° C for 1 hour and 150 ° C for 1 hour. Each code is as follows.
A: Conductivity was obtained with 20/20 semiconductor devices.
A: Conductivity was obtained with 18 to 19/20 semiconductor devices.
(Triangle | delta): Conductivity was able to be taken with the semiconductor device of 16-17 / 20.
X: Conductivity was obtained with a semiconductor device of 16 or less / 20.

2. Reflow resistance Reflow resistance was evaluated by a scanning ultrasonic flaw detector (SAT) after performing moisture absorption treatment on the obtained semiconductor device at 85 ° C./85% RH / 168 hours, and performing IR reflow at 260 ° C. three times. .
Each code is as follows.
(Double-circle): There was no crack at all.
A: The number of cracks generated was 2 or less.
Δ: The number of cracks generated was 3 or more and 5 or less.
X: The number of cracks generated was 6 or more.

3. Productivity The productivity of other examples and comparative examples was compared using the production man-hour of comparative example 1 as a reference (100). Each code is as follows. In addition,-in a table | surface shows that it was not able to evaluate.
A: Production man-hours of Comparative Example 3 were 40 or more and less than 60 with the production man-hours of Comparative Example 3 as a reference (100).
A: The production man-hours of Comparative Example 3 were 60 or more and less than 80 with the production man-hours of Comparative Example 3 as a reference (100).
(Triangle | delta): The production man-hour of the comparative example 3 was 80 or more and less than 100 on the basis (100).
X: The production man-hour of Comparative Example 3 was 100 or more with the production man-hour of the comparative example 3 as a standard (100).

As is apparent from Table 1, Examples 1 to 4 were excellent in connection reliability, and it was suggested that a semiconductor element having a through electrode and another semiconductor element can be suitably bonded.
Moreover, it was shown that Examples 1-4 are excellent also in productivity.
Further, in the method of pouring the liquid sealing resin between the semiconductor element and the substrate as in Comparative Example 1, it is difficult to pour between the narrow pitch as described above, the filling property becomes insufficient, and the reliability is lowered. Was shown to do.

FIG. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention. FIG. 2 is a cross-sectional view showing an example of a method for manufacturing a semiconductor device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st semiconductor element 10 Board | substrate 11 Solder bump 12 2nd adhesive layer 12 'Resin layer 13 Conductor part 14 Functional surface 2 2nd semiconductor element 21 Solder bump 22 1st adhesive layer 23 Conductor part 24 Functional surface 5 Support base material 51 Support Base Material 6 Adhesive Layer 7 Laminate 8 Semiconductor Wafer 81 Conductor Part 100 Semiconductor Device

Claims (7)

A semiconductor device comprising: a substrate; a first semiconductor element provided on at least one surface side of the substrate; and a second semiconductor element having a conductor portion penetrating in the thickness direction.
The first semiconductor element and the second semiconductor element are electrically connected via a protruding electrode;
Between the first semiconductor element and the second semiconductor element, a first adhesive layer made of a cured product of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity is disposed. A semiconductor device.   The substrate and the first semiconductor element are electrically connected via a protruding electrode, and a resin capable of crosslinking reaction and a flux activity are provided between the substrate and the first semiconductor element. The semiconductor device according to claim 1, wherein a second adhesive layer composed of a cured product of a resin composition containing a compound is disposed.   The semiconductor device according to claim 1, wherein the resin composition further contains a film-forming resin.   4. The semiconductor device according to claim 1, wherein the compound having flux activity is a compound having at least one of a carboxyl group and a phenolic hydroxyl group.   5. The semiconductor device according to claim 1, wherein the compound having the flux activity is capable of acting as a curing agent for the resin capable of crosslinking reaction. 6. Disposing a layer composed of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity and a dicing sheet layer on one surface of a semiconductor wafer having a plurality of conductor portions penetrating in the thickness direction; ,
Separating the semiconductor wafer into individual pieces to obtain a second semiconductor element having a conductor portion penetrating in the thickness direction;
Picking up the second semiconductor element from a dicing sheet layer in a state having a layer composed of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity;
And mounting the picked-up second semiconductor element on the other surface side of the first semiconductor element mounted on one surface side of the substrate.   The first semiconductor element and the substrate are bonded in advance with a second adhesive layer made of a cured product of a resin composition containing a resin capable of crosslinking reaction and a compound having flux activity. Item 7. A method for manufacturing a semiconductor device according to Item 6.

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