阅读说明：本技术 密封用树脂组合物、半导体封装体及半导体封装体的制造方法 (Resin composition for sealing, semiconductor package, and method for producing semiconductor package ) 是由 平井友贵 井上英俊 于 2018-06-29 设计创作，主要内容包括：本发明提供一种密封用树脂组合物,其含有环氧树脂、固化剂和填充材料,所述环氧树脂含有双酚型环氧树脂和1,6－双(缩水甘油基氧基)萘,1,6－双(缩水甘油基氧基)萘在所述环氧树脂整体中所占的比例为10质量％～30质量％。(The present invention provides a resin composition for sealing, which contains an epoxy resin, a curing agent and a filler, wherein the epoxy resin contains a bisphenol epoxy resin and 1, 6-bis (glycidyloxy) naphthalene, and the proportion of the 1, 6-bis (glycidyloxy) naphthalene in the entire epoxy resin is 10 to 30% by mass.)

1. A resin composition for sealing, which contains an epoxy resin, a curing agent and a filler, wherein the epoxy resin contains a bisphenol epoxy resin and 1, 6-bis (glycidyloxy) naphthalene, and the proportion of the 1, 6-bis (glycidyloxy) naphthalene in the entire epoxy resin is 10 to 30% by mass.

2. The sealing resin composition according to claim 1, wherein the bisphenol epoxy resin contains a bisphenol F epoxy resin.

3. The sealing resin composition according to claim 1 or 2, wherein the bisphenol epoxy resin accounts for 20 mass% or more and less than 90 mass% of the entire epoxy resin.

4. The sealing resin composition according to any one of claims 1 to 3, wherein the epoxy resin further contains a glycidyl amine type epoxy resin.

5. The sealing resin composition according to claim 4, wherein the glycidyl amine type epoxy resin contains a trifunctional or higher glycidyl amine type epoxy resin.

6. The sealing resin composition according to claim 4 or 5, wherein the glycidyl amine type epoxy resin accounts for 10 to 60 mass% of the total epoxy resin.

7. A semiconductor package comprising a support, a semiconductor element disposed on the support, and a cured product of the sealing resin composition according to any one of claims 1 to 6 for sealing the semiconductor element.

8. A method of manufacturing a semiconductor package, comprising:

a step of filling a gap between a support and a semiconductor element disposed on the support with the sealing resin composition according to any one of claims 1 to 6; and a step of curing the sealing resin composition.

Technical Field

The invention relates to a sealing resin composition, a semiconductor package and a method for manufacturing the semiconductor package.

Background

Conventionally, the main performance improvement of a liquid sealing material (underfill material) used in the flip-chip type semiconductor mounting technology has been oriented to how to meet various requirements such as fine pitch of a wiring pattern (improvement of injection property) while maintaining the reliability of a semiconductor package at a high level. For example, patent document 1 describes a liquid sealing material in which a bisphenol epoxy resin is blended with a specific amount of an aminophenol epoxy resin, thereby achieving good injection properties and fillet crack suppression after sealing.

Disclosure of Invention

Problems to be solved by the invention

In recent years, with the progress of increasing the size of semiconductor packages, the sealing area tends to increase. Accordingly, the possibility that an increase in stress generated between the sealing portion and the substrate in the package may affect the reliability of the package is increased. Therefore, from the viewpoint of suppressing the stress generated inside the package, the importance of the design of the sealing material is considered to increase in the future.

In view of the above circumstances, an object of the present invention is to provide a resin composition for sealing which has excellent injectability and an excellent effect of suppressing stress generated inside a package, a semiconductor package obtained using the resin composition, and a method for producing the semiconductor package.

Means for solving the problems

Means for solving the above problems include the following embodiments.

< 1 > a sealing resin composition comprising an epoxy resin, a curing agent and a filler, wherein the epoxy resin comprises a bisphenol epoxy resin and 1, 6-bis (glycidyloxy) naphthalene, and the proportion of the 1, 6-bis (glycidyloxy) naphthalene in the whole epoxy resin is 10 to 30% by mass.

< 2 > the sealing resin composition according to < 1 >, wherein the bisphenol epoxy resin contains a bisphenol F epoxy resin.

< 3 > the sealing resin composition according to < 1 > or < 2 >, wherein the bisphenol epoxy resin accounts for 20 mass% or more and less than 90 mass% of the total epoxy resin.

< 4 > the sealing resin composition according to any one of < 1 > to < 3 >, wherein the epoxy resin further contains a glycidyl amine type epoxy resin.

< 5 > the sealing resin composition according to < 4 >, wherein the glycidyl amine type epoxy resin contains a trifunctional or higher glycidyl amine type epoxy resin.

< 6 > the sealing resin composition according to < 4 > or < 5 >, wherein the glycidyl amine type epoxy resin accounts for 10 to 60 mass% of the total epoxy resin.

< 7 > a semiconductor package comprising a support, a semiconductor element disposed on the support, and a cured product of the sealing resin composition described in any one of < 1 > -6 > for sealing the semiconductor element.

< 8 > a method for manufacturing a semiconductor package, comprising:

filling a gap between a support and a semiconductor element disposed on the support with the sealing resin composition described in any one of < 1 > -6 >; and curing the sealing resin composition.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a sealing resin composition having excellent injectability and an excellent effect of suppressing stress generated inside a package, a semiconductor package obtained using the sealing resin composition, and a method for producing the semiconductor package.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not essential unless otherwise explicitly stated. Numerical values and ranges thereof are also the same and do not limit the invention.

In the present disclosure, the term "step" includes a step that is independent from other steps, and includes a step as long as the purpose of the step is achieved even when the step cannot be clearly distinguished from other steps.

In the present disclosure, in the numerical range represented by the term "to", the numerical values before and after the term "to" are included as the minimum value and the maximum value, respectively.

In the present disclosure, in the numerical ranges recited in the stepwise manner, the upper limit value or the lower limit value recited in one numerical range may be replaced with the upper limit value or the lower limit value recited in another numerical range recited in the stepwise manner. In the numerical ranges recited in the present invention, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.

In the present disclosure, each ingredient may contain two or more substances in accordance therewith. When two or more substances corresponding to each component are present in the composition, the content ratio or content of each component refers to the total content ratio or content of the two or more substances present in the composition unless otherwise specified.

In the present disclosure, two or more kinds of particles corresponding to each component may be contained. When two or more kinds of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value related to a mixture of the two or more kinds of particles present in the composition unless otherwise specified.

< resin composition for sealing >

The resin composition for sealing of the present embodiment contains an epoxy resin containing a bisphenol-type epoxy resin and 1, 6-bis (glycidyloxy) naphthalene (an epoxy resin represented by the following formula (1); hereinafter also referred to as a specific naphthalene-type epoxy resin), a curing agent, and a filler, and the specific naphthalene-type epoxy resin accounts for 10 to 30% by mass of the entire epoxy resin.

[ solution 1]

The present inventors found, as a result of their studies, that: the resin composition for sealing, which contains a bisphenol epoxy resin and a specific naphthalene epoxy resin as epoxy resins and in which the specific naphthalene epoxy resin accounts for 10 to 30 mass% of the total epoxy resins, has excellent injectability, a low coefficient of thermal expansion in the cured state, and a low elastic modulus.

It is considered that when the thermal expansion coefficient of the sealing resin composition in a cured state is low, the difference in thermal expansion coefficient between the cured product and the support becomes small, and the effect of reducing the stress generated can be obtained. Further, it is considered that if the sealing resin composition has a low elastic modulus in a cured state, an effect of relaxing the generated stress can be obtained.

Further, the sealing resin composition of the present embodiment can suppress an increase in viscosity before curing and reduce the thermal expansion coefficient and the elastic modulus after curing, compared with a method of increasing the amount of a filler or adding a flexibility agent, and thus it is considered that both favorable injectability and a stress reduction or relaxation effect can be achieved.

The reason why the sealing resin composition having the above-mentioned structure has a low thermal expansion coefficient and a low elastic modulus in a cured state is not clear, but is presumed to be: by containing the specific naphthalene type epoxy resin as the epoxy resin, the thermal expansion coefficient is reduced, and by suppressing the amount of the specific naphthalene type epoxy resin to a certain ratio or less and by using the bisphenol type epoxy resin in combination, the elastic modulus is maintained low.

The sealing resin composition is preferably in a liquid state at the time of use. More specifically, the viscosity at 25 ℃ (viscosity at 10 rpm) is preferably 25 pas or less. The viscosity at 110 ℃ is preferably 0.12 pas or less. The viscosity of the sealing resin composition is a value measured by the method described in the examples described later.

[ epoxy resin ]

The specific naphthalene epoxy resin is an epoxy resin which is liquid at room temperature (25 ℃), and is also available as a commercially available product. The commercially available product may be, for example, the product name "Epiclon HP-4032D" available from DIC.

From the viewpoint of reducing the thermal expansion coefficient, the proportion of the specific naphthalene-type epoxy resin in the entire epoxy resin is 10 mass% or more, preferably 15 mass% or more. From the viewpoint of maintaining the injectability well, the proportion of the specific naphthalene-type epoxy resin in the entire epoxy resin is 30 mass% or less, preferably 25 mass% or less.

The type of bisphenol epoxy resin is not particularly limited, and bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, and the like can be mentioned. The bisphenol epoxy resin contained in the sealing resin composition may be only one kind or two or more kinds. From the viewpoint of using the sealing resin composition in a liquid state, it is preferable that the bisphenol epoxy resin is in a liquid state at room temperature (25 ℃). The bisphenol type epoxy resin is preferably a bisphenol F type epoxy resin from the viewpoint of reducing the viscosity.

The ratio of the bisphenol epoxy resin in the entire epoxy resin is not particularly limited, and may be selected according to the desired properties of the sealing resin composition. For example, the content may be selected from a range of 20% by mass or more and less than 90% by mass, or may be selected from a range of 30% by mass to 80% by mass.

The sealing resin composition may contain an epoxy resin other than the specific naphthalene-type epoxy resin and the bisphenol-type epoxy resin.

The type of the epoxy resin other than the specific naphthalene-type epoxy resin and the bisphenol-type epoxy resin is not particularly limited, and may be selected according to the desired characteristics of the sealing resin composition. Specifically, there may be mentioned: epoxy resins obtained by epoxidizing a phenol novolac resin obtained by condensing or co-condensing a phenolic compound selected from at least 1 of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, and the like, and naphthol compounds such as α -naphthol, β -naphthol, dihydroxynaphthalene, and the like, and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, and the like, in an acidic catalyst, that is, a phenol novolac type epoxy resin (such as a phenol novolac type epoxy resin, an o-cresol novolac type epoxy resin, and the like); an epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst, that is, a triphenylmethane type epoxy resin; an epoxy resin obtained by epoxidizing a phenol novolac resin obtained by co-condensing the phenol compound, the naphthol compound and the aldehyde compound with an acidic catalyst, that is, a copolymer epoxy resin; diglycidyl ethers of alkyl-substituted or unsubstituted diphenols, i.e. biphenyl-type epoxy resins; diglycidyl ethers of stilbene-based phenol compounds, i.e., stilbene-type epoxy resins; diglycidyl ethers of bisphenol S and the like, that is, epoxy resins containing a sulfur atom; epoxy resins as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins, which are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl amine type epoxy resins, which are epoxy resins obtained by substituting an active hydrogen bonded to a nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, or the like with a glycidyl group; epoxy resin obtained by epoxidizing co-condensation resin of dicyclopentadiene and phenol compound, namely dicyclopentadiene type epoxy resin; alicyclic epoxy resins such as vinylcyclohexene dioxide, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane, which are epoxy resins obtained by epoxidizing intramolecular ethylenic bonds; glycidyl ether of p-xylene-modified phenolic resin, namely p-xylene-modified epoxy resin; glycidyl ether of m-xylene-modified phenolic resin, i.e., m-xylene-modified epoxy resin; glycidyl ethers of terpene-modified phenolic resins, i.e., terpene-modified epoxy resins; glycidyl ether of dicyclopentadiene-modified phenol resin, i.e., dicyclopentadiene-modified epoxy resin; glycidyl ether of cyclopentadiene-modified phenol resin, namely cyclopentadiene-modified epoxy resin; glycidyl ether of polycyclic aromatic ring modified phenolic resin, namely polycyclic aromatic ring modified epoxy resin; glycidyl ethers of phenolic resins containing naphthalene rings, namely naphthalene-type epoxy resins; a halogenated phenol novolac type epoxy resin; p-phenylene bisphenol type epoxy resin; trimethylolpropane type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; an aralkyl type epoxy resin, which is an epoxy resin obtained by epoxidizing an aralkyl type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; and the like. These epoxy resins may be used alone or in combination of two or more.

When the sealing resin composition contains a bisphenol epoxy resin and an epoxy resin other than the bisphenol epoxy resin as the epoxy resin other than the specific naphthalene epoxy resin, the mass ratio of the bisphenol epoxy resin to the epoxy resin other than the bisphenol epoxy resin (bisphenol epoxy resin/epoxy resin other than the bisphenol epoxy resin) is not particularly limited. For example, the concentration of the surfactant can be selected from the range of 1/5-5/1.

When the sealing resin composition contains the bisphenol epoxy resin and the epoxy resin other than the bisphenol epoxy resin as the epoxy resin other than the specific naphthalene epoxy resin, the sealing resin composition preferably contains an epoxy resin that is liquid at room temperature (25 ℃) and more preferably contains a glycidyl amine epoxy resin, from the viewpoint of using the sealing resin composition in a liquid state. From the viewpoint of reducing the viscosity of the sealing resin composition, the glycidyl amine type epoxy resin preferably has a molecular weight of 300 or less.

The glycidyl amine type epoxy resin may be bifunctional or trifunctional or more. From the viewpoint of improving heat resistance after curing, a trifunctional or higher (3 or higher epoxy groups in 1 molecule) glycidyl amine type epoxy resin is preferable. Examples of the difunctional or higher glycidylamine-type epoxy resin include N, N-diglycidylaniline and N, N-diglycidylanthro-toluidine. Examples of the trifunctional or higher glycidyl amine type epoxy resin include triglycidyl p-aminophenol, 4' -methylenebis [ N, N-bis (oxiranylmethyl) aniline ], and the like. Among them, triglycidyl p-aminophenol is preferable from the viewpoint of viscosity at room temperature (25 ℃).

When the sealing resin composition contains a glycidyl amine type epoxy resin as the epoxy resin, the proportion thereof is not particularly limited. For example, the proportion of the epoxy resin in the entire epoxy resin is preferably 10 to 60% by mass.

[ curing agent ]

The type of the curing agent is not particularly limited, and may be selected according to the desired properties of the sealing resin composition. For example, there may be mentioned: amine curing agents, phenol curing agents, anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like. One curing agent may be used alone, or two or more curing agents may be used in combination.

From the viewpoint of using the sealing resin composition in a liquid state, the curing agent is preferably an amine curing agent. Examples of the amine curing agent include: aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4 '-diamino-dicyclohexylmethane, aromatic amine compounds such as 4, 4' -diaminodiphenylmethane and 2-methylaniline, imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole, and imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline.

The equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent (active hydrogen in the case of an amine curing agent) to the number of functional groups in the epoxy resin (number of functional groups in the curing agent/number of functional groups in the epoxy resin) is not particularly limited. From the viewpoint of suppressing the amount of unreacted components, the amount is preferably set to a range of 0.5 to 2.0, and more preferably 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, the range of 0.8 to 1.2 is more preferable.

[ Filler ]

The kind of the filler is not particularly limited. Specifically, there may be mentioned: inorganic materials such as silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, and mica. A filler material having a flame retardant effect may also be used. Examples of the filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxide of magnesium and zinc, zinc borate, and the like.

Among the above fillers, silica is preferable from the viewpoint of reducing the thermal expansion coefficient, and alumina is preferable from the viewpoint of improving the thermal conductivity. The filler may be used alone or in combination of two or more.

The content of the filler contained in the sealing resin composition is not particularly limited. From the viewpoint of satisfying both good fluidity and curing of the filler, the content of the filler is preferably 30 to 90% by mass, more preferably 50 to 75% by mass, of the entire sealing resin composition.

When the filler is in the form of particles, the average particle diameter thereof is not particularly limited. For example, the volume average particle diameter is preferably 0.2 to 20 μm, more preferably 0.5 to 15 μm. When the volume average particle diameter is 0.2 μm or more, the increase in viscosity of the sealing resin composition tends to be further suppressed. When the volume average particle diameter is 20 μm or less, the filling property into a narrow gap tends to be further improved. The volume average particle size of the filler material may be determined in the form of a particle size (D50), which particle size (D50) refers to: the particle size at which the volume accumulation from the small diameter side reaches 50% in the volume-based particle size distribution obtained by the laser scattering diffraction particle size distribution measuring apparatus.

[ various additives ]

The sealing resin composition may contain various additives such as a curing accelerator, a stress relaxation agent, a coupling agent, a release agent, and a colorant in addition to the above components. The sealing resin composition may contain, in addition to the additives exemplified below, various additives known in the art as needed.

(curing accelerators)

The sealing resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and may be selected according to the type of the epoxy resin and the curing agent, the desired properties of the sealing resin composition, and the like.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the curable resin component (total of the epoxy resin and the curing agent).

(stress-relieving agent)

The sealing resin composition may contain a stress relaxation agent. Examples of the stress relaxation agent include particles of thermoplastic elastomer, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, silicone rubber, and the like. The stress relaxation agent may be used alone or in combination of two or more.

When the sealing resin composition contains the stress relaxation agent, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the curable resin component (total of the epoxy resin and the curing agent).

(coupling agent)

The sealing resin composition may contain a coupling agent. Examples of coupling agents include: silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, and the like. Among them, a silane compound is preferable from the viewpoint of fluidity. One kind of coupling agent may be used alone, or two or more kinds may be used in combination.

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the filler.

(coloring agent)

The sealing resin composition may contain a colorant. Examples of the colorant include: carbon black, organic dyes, organic pigments, titanium oxide, red lead and the like. The colorant may be used alone or in combination of two or more.

When the sealing resin composition contains a colorant, the amount thereof is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the curable resin component (total of the epoxy resin and the curing agent).

(use of the sealing resin composition)

The sealing resin composition can be used in various mounting techniques. In particular, it can be suitably used as an underfill material used in flip-chip type mounting technology. For example, the present invention can be suitably used for filling a gap between a semiconductor element bonded with a bump or the like and a support.

The type of the semiconductor element and the support is not particularly limited, and may be selected from those generally used in the field of semiconductor packages. The method of filling the gap between the semiconductor element and the support with the sealing resin composition is not particularly limited. For example, the reaction can be carried out by a known method using a dispenser or the like.

< semiconductor Package >

The semiconductor package of the present embodiment includes a support, a semiconductor element disposed on the support, and a cured product of the sealing resin composition sealing the semiconductor element.

In the above semiconductor package, the types of the semiconductor element and the support are not particularly limited, and may be selected from those generally used in the field of semiconductor packages. The cured product of the resin composition for encapsulating the semiconductor package has a low coefficient of thermal expansion and a low elastic modulus. Therefore, when stress is generated between the cured product of the sealing resin composition and the support, the effect of suppressing stress is excellent.

< method for manufacturing semiconductor Package >

The method for manufacturing a semiconductor package according to the present embodiment includes: filling a gap between a support and a semiconductor element disposed on the support with the sealing resin composition; and curing the sealing resin composition.

In the above method, the kind of the semiconductor element and the support is not particularly limited, and may be selected from those generally used in the field of semiconductor packages. The method of filling the gap between the semiconductor element and the support with the sealing resin composition and the method of curing the sealing resin composition after filling are not particularly limited, and can be carried out by a known method.