KR102695061B1 - Adhesive composition for semiconductor package and adhesive film containing the same - Google Patents

Abstract

The present invention relates to an adhesive composition for a semiconductor package and an adhesive film comprising the same. The adhesive composition for a semiconductor package according to the present invention reduces the occurrence of resin traps during thermal compression bonding of a semiconductor element, thereby enabling improvement of the connectivity and reliability of the semiconductor element.

Description

{ADHESIVE COMPOSITION FOR SEMICONDUCTOR PACKAGE AND ADHESIVE FILM CONTAINING THE SAME}

The present invention relates to an adhesive composition for a semiconductor package and an adhesive film including the same.

Semiconductor packaging technology aims to connect signals between semiconductor devices and protect them from natural, chemical, and thermal environmental changes.

Recently, the need for high density and high integration of semiconductor packages has been increasing. Accordingly, the size of semiconductor chips is gradually increasing, and the stack package method of stacking semiconductor chips in multiple stages is being widely applied to improve integration.

Thermal compression bonding is mainly used for bonding semiconductor chips. Thermal compression bonding is a process that is performed under high temperature and high pressure conditions and induces connection of semiconductor elements within a few seconds.

Through the thermal compression bonding process, the semiconductor package melts the bumps of the semiconductor elements and, through the joining process, induces connection between the semiconductor elements. In order to induce connection between these semiconductor elements, it is essential to make an appropriate connection, such as inserting a film for the semiconductor package between the upper and lower bumps of the semiconductor elements.

However, there is a problem that defects such as resin traps occur in the film for semiconductor packaging during this thermal compression bonding process, which reduces the connectivity and reliability of semiconductor elements.

The present invention provides an adhesive composition for a semiconductor package that enables improvement of the connectivity and reliability of a semiconductor device during thermal compression bonding of the semiconductor device.

In addition, the present invention provides an adhesive film including the adhesive composition for the semiconductor package.

According to one embodiment of the present invention,

(a) phenol resin,

(b) epoxy resin,

(c) (meth)acrylate resin, and

(d) Filler comprising inorganic particles surface-modified by a silane compound having a carboxylic acid terminal group;

An adhesive composition for a semiconductor package, including:

In addition, according to another embodiment of the present invention, an adhesive film including the adhesive composition for a semiconductor package is provided.

Hereinafter, an adhesive composition for a semiconductor package according to implementation examples of the present invention and an adhesive film including the same will be described in more detail.

Unless explicitly stated otherwise in this specification, terminology is used only to describe particular embodiments and is not intended to limit the invention.

As used herein, the singular forms include the plural forms as well, unless the phrases clearly indicate the opposite.

The term "including" as used herein specifies a particular characteristic, region, integer, step, operation, element, and/or component, but does not exclude the presence or addition of any other particular characteristic, region, integer, step, operation, element, component, and/or group.

As a result of continued research by the present inventors, it has been confirmed that an adhesive composition for a semiconductor package including an inorganic filler surface-modified with a phenol resin, an epoxy resin, a (meth)acrylate-based resin, and a silane compound having a carboxylic acid terminal group reduces the occurrence of resin traps during thermocompression bonding to a semiconductor element, thereby enabling improvement in the connectivity and reliability of the semiconductor element.

I. Adhesive composition for semiconductor package

According to one embodiment of the invention,

(a) phenol resin,

(b) epoxy resin,

(c) (meth)acrylate resin, and

(d) Filler comprising inorganic particles surface-modified by a silane compound having a carboxylic acid terminal group;

An adhesive composition for a semiconductor package, including:

The adhesive composition for the above semiconductor package includes (a) a phenol resin as a thermosetting binder.

Preferably, the phenol resin may have a softening point of 105° C. or higher, or from 105° C. to 150° C., or from 105° C. to 130° C. By including a phenol resin having a softening point of 105° C. or higher, the adhesive composition for a semiconductor package can have sufficient heat resistance, strength, and adhesiveness after curing.

If the softening point of the phenol resin is too low, the adhesive composition for semiconductor packages may not obtain a cured product having sufficient strength after curing. In addition, if the softening point of the phenol resin is too high, the fluidity of the adhesive composition for semiconductor packages may increase, which may create voids inside the adhesive during an actual semiconductor manufacturing process, thereby significantly reducing the reliability or quality of the final product.

Preferably, the phenol resin may be at least one compound selected from the group consisting of a bisphenol A novolac resin having a softening point of 105° C. or higher and a biphenyl novolac resin having a softening point of 105° C. or higher.

Based on the total weight of the adhesive composition for the semiconductor package, the phenol resin may be included in an amount of 10 to 15 wt%, or 12 to 15 wt%, or 12 to 14 wt%.

The adhesive composition for the above semiconductor package includes (b) an epoxy resin as a thermosetting binder.

The above epoxy resin enables the adhesive composition for the semiconductor package to have adhesive strength or adhesion, and when the adhesive composition for the semiconductor package is cured, it forms a cross-linking structure with other components to secure mechanical properties, heat resistance, and impact resistance of the finally manufactured adhesive film.

Preferably, the epoxy resin may have a softening point of 70° C. or higher, or 70° C. to 120° C.

If the softening point of the epoxy resin is too low, it is difficult for the adhesive composition for semiconductor packages to secure sufficient modulus at high temperatures after curing, the adhesive strength to the substrate also has a large variation depending on the temperature, and the adhesive strength of the adhesive composition for semiconductor packages increases, which may deteriorate chip pick-up performance after dicing.

As the above epoxy resin, any type of compound well known in the technical field to which the present invention belongs can be applied without any particular limitation.

For example, the epoxy resin may be at least one resin selected from the group consisting of bisphenol-based epoxy resins, biphenyl-based epoxy resins, naphthalene-based epoxy resins, fluorene-based epoxy resins, phenol novolac-based epoxy resins, cresol novolac-based epoxy resins, xyloc-based epoxy resins, trishydroxylphenylmethane-based epoxy resins, tetraphenylmethane-based epoxy resins, dicyclopentadiene-based epoxy resins, and dicyclopentadiene-modified phenol-based epoxy resins.

Examples of the above bisphenol-based epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol AF type epoxy resin.

The above epoxy resin may have an average epoxy equivalent of 100 g/eq. to 1,000 g/eq. The average epoxy equivalent is a value calculated based on the weight ratio and epoxy equivalent of each epoxy resin included in the epoxy resin.

Based on the total weight of the adhesive composition for the semiconductor package, the epoxy resin may be included in an amount of 10 to 15 wt%, or 12 to 15 wt%, or 12 to 14 wt%.

The adhesive composition for the above semiconductor package includes (c) a (meth)acrylate resin.

As used herein, “(meth)acrylic” is intended to include both “acrylic” and “methacrylic”.

Preferably, the (meth)acrylate-based resin may be a (meth)acrylic acid ester polymer containing 15 wt% or more, or 15 to 35 wt%, or 15 to 20 wt%, of (meth)acrylate-based repeating units including an epoxy-based functional group among the entire repeating units or segments of the polymer.

The (meth)acrylate resin containing 15 wt% or more of a (meth)acrylate repeating unit including the above-mentioned epoxy functional group enables the components included in the adhesive composition for the semiconductor package to bind to each other during curing, thereby ensuring a higher degree of curing, and enables the adhesive film formed by curing the adhesive composition for the semiconductor package to secure sufficient mechanical properties.

Specifically, since the (meth)acrylate-based repeating unit having an epoxy functional group introduced therein is 15 wt% or more among the total repeating units of the (meth)acrylate-based resin, the adhesive composition for a semiconductor package can form a more cross-linked structure after curing, and the compatibility between the (meth)acrylate-based resin and the epoxy resin can be improved. Accordingly, the finally manufactured adhesive film can have more homogeneous physical properties and appearance characteristics, and improved mechanical properties, heat resistance, and impact resistance.

The above epoxy functional group can be substituted one or more times in the repeating unit forming the main chain of the (meth)acrylate resin.

The above epoxy functional group may include an epoxy group or a glycidyl group.

If the content of the (meth)acrylate repeating unit including the epoxy functional group among the above (meth)acrylate resins is too small, the heat resistance and impact resistance of the adhesive film obtained using the above adhesive composition for semiconductor packages may not be sufficient.

The upper limit of the content of (meth)acrylate repeating units including epoxy functional groups among the above (meth)acrylate resins is not significantly restricted. However, considering the elasticity and adhesiveness of the finally manufactured adhesive film, it is preferable that the (meth)acrylate repeating units having epoxy functional groups introduced are 35 wt% or less among the total repeating units of the (meth)acrylate resins.

The (meth)acrylate-based resin containing 15 wt% or more of a (meth)acrylate-based repeating unit including the above-described epoxy-based functional group may have a glass transition temperature of -10° C. to 20° C., or -5° C. to 15° C. By using the (meth)acrylate-based resin having the above-described glass transition temperature, the adhesive composition for the semiconductor package may have sufficient fluidity, and the finally manufactured adhesive film may secure high adhesive strength.

Based on the total weight of the adhesive composition for the semiconductor package, the (meth)acrylate resin may be included in an amount of 25 to 40 wt%, or 30 to 40 wt%, or 35 to 40 wt%.

The adhesive composition for the above semiconductor package includes (d) a filler.

In particular, the filler comprises an inorganic particle surface-modified with a silane compound having a carboxylic acid terminal group.

For example, the surface-modified inorganic particles may have a structure as represented by Chemical Formula 1 below.

[Chemical Formula 1]

In the above chemical formula 1,

R ¹ and R ² are each independently an alkylene group having 1 to 10 carbon atoms,

X is -NH-, -S-, or -O-.

The above chemical formula 1 exemplifies one functional group introduced onto the surface of the surface-modified inorganic particle. In fact, the surface of the surface-modified inorganic particle is covered with functional groups having a structure shown in the above chemical formula 1.

As shown in the chemical formula 1 above, the surface-modified inorganic particle includes a carboxylic acid terminal group bonded via a silane compound on the surface of any inorganic particle.

The surface-modified inorganic particles satisfying these structures are included in the adhesive composition for the semiconductor package, and can minimize the occurrence of defects such as resin traps during thermal compression bonding of a semiconductor device to which the adhesive composition is applied.

As a non-limiting example, the surface-modified inorganic particle can be prepared by reacting an inorganic particle having a hydroxyl group (-OH) on the surface with a silane compound and then introducing a carboxylic acid group to the terminal of the silane compound.

As a non-limiting example, the surface-modified inorganic particles may include:

(1) A step for preparing an inorganic particle dispersion by dispersing inorganic particles having hydroxyl groups on the surface in an alcohol solvent such as methanol, ethanol, or propanol;

(2) A step of preparing a mixed solution by mixing a silane compound having an amine group terminal in the inorganic particle dispersion of step (1) at a weight ratio of 1:0.1 to 1:1 with respect to the inorganic particles;

(3) A step of stirring the mixed solution of step (2) for 1 to 12 hours, then separating and washing the solid content to obtain inorganic particles having a surface treated with a silane compound;

(4) A step of dispersing the surface-treated inorganic particles of step (3) in a polar aprotic solvent;

(5) A step of preparing a solution of succinic anhydride dissolved in a polar aprotic solvent, separately from the above step (4); and

(6) A step of adding the solution of step (5) dropwise to the solution of step (4) above, reacting at 60 to 80°C for 12 to 24 hours, and then separating and washing the solid to obtain inorganic particles surface-modified by a silane compound having a carboxylic acid terminal group.

can be prepared in a manner that includes:

As the above inorganic particles, one or more types of particles selected from the group consisting of silica (SiO ₂ ), zinc oxide (ZnO), and zirconium oxide (ZrO ₂ ) can be used.

It is preferable that the above-mentioned inorganic particles have a moisture level of 10 to 80% according to the standard test method of DIN EN ISO 787-2.

The above-mentioned function ratio measurement method is performed by measuring the volatile component content (hereinafter referred to as moisture content) of the inorganic particles after drying the inorganic particles at 105°C for 2 hours based on DIN EN ISO 787-2. At this time, the drying loss is generally mainly composed of moisture.

For example, 10 g of the above-described inorganic particles are weighed to an accuracy of 0.1 mg (sample weight E) in a dry glass weighing vessel (diameter 8 cm, height 3 cm) with an opaque glass lid. With the glass lid open, the sample is dried in a drying cabinet at 105 ± 2 ° C. for 2 hours. Then, the glass weighing vessel is sealed and cooled to room temperature in a desiccator cabinet using silica gel as a desiccant. The sample is weighed to obtain the final weight A. The moisture content (%) is determined by [(E (g) - A (g)) * 100%] / [E (g)].

Specifically, it is preferable that the inorganic particles have a moisture content of 10% or more, or 20% or more, or 30% or more. In order to allow the surface of the inorganic particles to be sufficiently modified, it is preferable that the moisture content of the inorganic particles is 10% or more.

However, if the surface of the inorganic particles is excessively modified, the filler may coagulate within the adhesive composition or the physical properties of the adhesive composition may deteriorate. Therefore, it is preferable that the inorganic particles have a moisture content of 80% or less, or 70% or less, or 60% or less, or 50% or less.

More preferably, the inorganic particles may have a moisture content of 10 to 80%, or 20 to 80%, or 20 to 70%, or 30 to 70%, or 30 to 60%, or 30 to 50%.

And, it is preferable that the inorganic particles have an average particle size of 50 to 550 nm. If the particle size of the inorganic particles is too small, the filler may easily aggregate in the adhesive composition. On the other hand, if the particle size of the inorganic particles is too large, damage to the semiconductor circuit and a decrease in the adhesiveness of the adhesive film may be caused by the filler. The particle size of the inorganic particles can be obtained by the BET method or a laser diffraction particle size distribution measurement method.

Meanwhile, the filler may further include inorganic particles that are not surface-treated.

For example, the filler may contain the surface-treated first inorganic particles and the non-surface-treated second inorganic particles in a weight ratio of 1:0.1 to 1:0.5. If the filler contains too much of the non-surface-treated second inorganic particles, the addition effect of the first inorganic particles may not be sufficiently expressed.

The size of the second inorganic particles that are not surface-treated is similar to the size of the first inorganic particles, and their type is not particularly limited. For example, as the second inorganic particles, one or more particles selected from the group consisting of alumina, silica, barium sulfate, magnesium hydroxide, magnesium carbonate, magnesium silicate, magnesium oxide, calcium silicate, calcium carbonate, calcium oxide, aluminum hydroxide, aluminum nitride, and aluminum borate can be applied.

An ion adsorbent capable of adsorbing ionic impurities to improve reliability can be used as the second inorganic particle. As the ion adsorbent, one or more particles selected from the group consisting of magnesium-based particles such as magnesium hydroxide, magnesium carbonate, magnesium silicate, and magnesium oxide, calcium silicate, calcium carbonate, calcium oxide, alumina, aluminum hydroxide, aluminum nitride, aluminum borate whiskers, zirconium-based inorganic particles, and antimony-bismuth-based inorganic particles can be applied.

The content of the above filler can be adjusted in consideration of the mechanical properties of the finally manufactured adhesive film and the effect of reducing the occurrence of resin traps.

For example, the filler may be included in an amount of 25 to 35 wt%, or 30 to 35 wt%, based on the total weight of the adhesive composition for the semiconductor package.

The adhesive composition for the above semiconductor package may further include a curing agent.

As the above-mentioned hardener, any compound known to be usable in the manufacture of an adhesive film for a semiconductor package can be applied without any special limitation.

For example, the curing agent may be at least one compound selected from the group consisting of amine compounds, acid anhydride compounds, amide compounds, and phenol compounds.

As the above amine compounds, diaminodiphenylmethane, diethylenetriamine, triethylenetetraamine, diaminodiphenylsulfone, isophoronediamine, etc. can be used.

As the above acid anhydride compounds, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. can be used.

As the above amide compounds, dicyandiamide, a dimer of linolenic acid, and a polyamide resin synthesized from ethylenediamine can be used.

As the above phenol compounds, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, and terpene diphenol can be used; phenol resins obtained by condensation of phenols with aldehydes, ketones, or dienes; phenols and/or modified products of phenol resins; halogenated phenols such as tetrabromobisphenol A and brominated phenol resins; imidazoles, BF3-amine complexes, and guanidine derivatives can be used.

The content of the above hardener can be adjusted in consideration of the mechanical properties of the adhesive film to be finally manufactured. For example,

Based on the total weight of the adhesive composition for the semiconductor package, the curing agent may be included in an amount of 0.1 to 1.0 wt%, or 0.5 to 1.0 wt%.

The adhesive composition for the semiconductor package may further include a curing catalyst which is at least one compound selected from the group consisting of a phosphorus compound, a boron compound, a phosphorus-boron compound, and an imidazole compound.

The above curing catalyst serves to promote the action of the curing agent or the curing of the adhesive composition for the semiconductor package, and any compound known to be used in the production of a semiconductor adhesive film can be used without any particular limitation.

The content of the curing catalyst can be adjusted in consideration of the content of the curing agent and the properties of the adhesive film finally manufactured. For example, the curing catalyst can be included in an amount of 0.1 to 1.0 wt%, or 0.5 to 1.0 wt%, based on the total weight of the adhesive composition for the semiconductor package.

The adhesive composition for the semiconductor package may further contain an organic solvent.

The content of the organic solvent may be determined in consideration of the properties of the adhesive composition and the adhesive film including the same, and the productivity of the manufacturing process thereof.

For example, the organic solvent may be included in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total of (a) phenol resin, (b) epoxy resin, (c) (meth)acrylate resin, and (d) filler.

The above organic solvent may be at least one compound selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

The above ester solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetic acid (e.g., methyl oxyacetate, ethyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

The above ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

The above ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.

The above aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, etc.

The above sulfoxide solvent may be dimethyl sulfoxide, etc.

The adhesive composition for a semiconductor package comprising the above-described components may have a melt viscosity of 15,000 to 17,000 Pa.s, or 15,500 to 17,000 Pa.s, or 15,500 to 16,500 Pa.s measured at a temperature of 120° C.

If the melt viscosity of the adhesive composition for the semiconductor package is too low, a phenomenon in which the adhesive film is excessively pressed during thermal compression bonding may be observed.

II. Adhesive film for semiconductor packaging

According to another embodiment of the invention, an adhesive film for a semiconductor package comprising the adhesive composition described above is provided.

The above-described adhesive film for a semiconductor package includes the adhesive composition for a semiconductor package of the above-described embodiment, thereby exhibiting excellent adhesive strength during thermal compression bonding of a semiconductor circuit while reducing the occurrence of resin traps, thereby enabling improvement of the connectivity and reliability of semiconductor elements.

FIG. 1 is a cross-sectional view showing a laminated configuration of an adhesive film for a semiconductor package according to embodiments of the invention.

Referring to (a) of Fig. 1, the adhesive film may have a configuration in which a support substrate (1) and an adhesive layer (2) are sequentially laminated.

Referring to Fig. 1 (b), the adhesive film may have a configuration in which a support substrate (1), an adhesive layer (2), and a protective film (3) are sequentially laminated.

Referring to (c) of Fig. 1, the adhesive film may have a configuration in which a support substrate (1), an adhesive layer (4), an adhesive layer (2), and a protective film (3) are sequentially laminated.

As the above-mentioned supporting material, a resin film having excellent heat resistance or chemical resistance; a crosslinked film obtained by crosslinking the resin constituting the resin film; or a film obtained by applying a silicone resin or the like to the surface of the resin film and then performing a peeling treatment, etc. can be used.

As the resin constituting the above resin film, polyolefins such as polyester, polyethylene, polypropylene, polybutene, and polybutadiene, vinyl chloride, ethylene-methacrylic acid copolymer, ethylene vinyl acetate copolymer, polyester, polyimide, polyethylene terephthalate, polyamide, and polyurethane can be applied.

The thickness of the above-mentioned supporting substrate is not particularly limited, but may be 3 to 400 ㎛, or 5 to 200 ㎛, or 10 to 150 ㎛.

The above adhesive layer is made of the above-described adhesive composition for semiconductor packages. The contents of the above-described adhesive composition are as described above.

If necessary, an adhesive layer may be interposed between the support substrate and the adhesive layer. As the adhesive layer, any one known in the art may be applied without special limitation.

The type of the above protective film is not particularly limited, and a plastic film known in this field can be applied. For example, the above protective film can be a plastic film including a resin such as low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, a random copolymer of polypropylene, a block copolymer of polypropylene, homopolypropylene, polymethylpentene, an ethylene-vinyl acetate copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ionomer copolymer, an ethylene-vinyl alcohol copolymer, polybutene, a copolymer of styrene, etc.

The adhesive film for the semiconductor package can be manufactured by a method of mixing the components of the adhesive composition, coating the same on a support substrate to a predetermined thickness to form an adhesive layer, and drying the adhesive layer.

Additionally, the adhesive film can be manufactured by a method of forming an adhesive layer on the support substrate and then laminating a protective film on the adhesive layer.

In addition, the adhesive film can be manufactured by a method of forming an adhesive layer on the support substrate and then sequentially laminating an adhesive layer and a protective film on the adhesive layer.

The method for forming an adhesive layer on the above-mentioned supporting substrate may be a method in which the adhesive composition is applied as is or after being diluted in an appropriate organic solvent onto the supporting substrate or a release film using a known means such as a comma coater, a gravure coater, a die coater, or a reverse coater, and then dried at a temperature of 60° C. to 200° C. for 10 seconds to 30 minutes.

If necessary, an aging process may be additionally performed to promote sufficient crosslinking reaction of the adhesive layer.

The thickness of the above adhesive layer can be adjusted within a range of 1 to 500 ㎛, or 5 to 100 ㎛, or 5 to 50 ㎛.

The adhesive composition for a semiconductor package according to the present invention reduces the occurrence of resin traps during thermal compression bonding of semiconductor elements, thereby enabling improvement of the connectivity and reliability of semiconductor elements.

FIG. 1 is a cross-sectional view showing a laminated configuration of an adhesive film for a semiconductor package according to embodiments of the invention.
FIG. 2 is an SEM image of a connection part of a semiconductor device according to Examples 1 and 2 of the present invention, taken using a scanning electron microscope.
Figure 3 is an SEM image of a connection part of a semiconductor device according to Comparative Examples 1 to 3 of the present invention, taken using a scanning electron microscope.
FIG. 4 is an SEM image of a connection part of a semiconductor device according to Reference Examples 1 to 3 of the present invention, taken using a scanning electron microscope.

Hereinafter, preferred embodiments are presented to help understand the invention. However, the following embodiments are only intended to illustrate the invention and do not limit the invention to these embodiments.

Manufacturing example 1

(Preparation of surface-modified silica particles)

A silica dispersion was prepared by ultrasonically dispersing 0.1 wt% silica particles (moisture content 10%, average particle size 300 nm, manufacturer: Denki Kagaku Kogyo) in ethyl alcohol.

A mixed solution was prepared by mixing 0.5 wt% of a silane coupling agent ((3-aminopropyl)triethoxysilane, manufacturer: Sigma-Aldrich) with the above silica dispersion.

The above mixed solution was stirred at high speed for 6 hours to perform silica surface treatment, and the solid content was separated and washed to obtain silica particles surface-modified with a silane compound.

A first solution in which silica particles surface-modified with the silane compound at 10 wt% relative to N,N-dimethylformamide were dispersed and a second solution in which 0.1 M succinic anhydride was dissolved relative to N,N-dimethylformamide were prepared, respectively.

The second solution was added drop wise onto the first solution, reacted at 70°C for 12 hours, and the solid was separated and washed to obtain silica particles surface-modified with a silane compound having a carboxylic acid terminal group.

Manufacturing example 2

(Preparation of surface-modified silica particles)

A silica dispersion was prepared by ultrasonically dispersing 0.1 wt% silica particles (moisture content 80%, average particle size 300 nm, manufacturer: Denki Kagaku Kogyo) in ethyl alcohol.

A mixed solution was prepared by mixing 0.5 wt% of a silane coupling agent ((3-aminopropyl)triethoxysilane, manufacturer: Sigma-Aldrich) with the above silica dispersion.

The above mixed solution was stirred at high speed for 12 hours to perform silica surface treatment, and the solid content was separated and washed to obtain silica particles surface-modified with a silane compound.

A first solution in which silica particles surface-modified with the silane compound at 10 wt% relative to N,N-dimethylformamide were dispersed and a second solution in which 0.1 M succinic anhydride was dissolved relative to N,N-dimethylformamide were prepared, respectively.

The second solution was added drop wise onto the first solution, reacted at 70°C for 12 hours, and the solid was separated and washed to obtain silica particles surface-modified with a silane compound having a carboxylic acid terminal group.

Comparative manufacturing example 1

(Preparation of surface-modified silica particles)

A silica dispersion was prepared by ultrasonically dispersing 0.1 wt% silica particles (moisture content 10%, average particle size 300 nm, manufacturer: Denki Kagaku Kogyo) in ethyl alcohol.

A mixed solution was prepared by mixing 0.5 wt% of carboxylic acid (manufacturer: Sigma-Aldrich) with the above silica dispersion.

The above mixed solution was stirred at high speed for 1 hour to perform silica surface treatment, and the solid content was separated and washed to obtain silica particles surface-modified with carboxylic acid.

Comparative manufacturing example 2

(Preparation of surface-modified silica particles)

A silica dispersion was prepared by ultrasonically dispersing 0.1 wt% silica particles (moisture content 10%, average particle size 300 nm, manufacturer: Denki Kagaku Kogyo) in ethyl alcohol.

A mixed solution was prepared by mixing 0.5 wt% of carboxylic acid (manufacturer: Sigma-Aldrich) with the above silica dispersion.

The above mixed solution was stirred at high speed for 12 hours to perform silica surface treatment, and the solid content was separated and washed to obtain silica particles surface-modified with carboxylic acid.

Examples 1 to 2, Comparative Examples 1 to 3, and Reference Examples 1 to 3

(1) Preparation of adhesive composition for semiconductor package

An adhesive composition was prepared by dissolving the components listed in Tables 1 to 3 below in methyl ethyl ketone.

(2) Manufacturing of adhesive film

The adhesive composition was applied onto a polyethylene terephthalate film (thickness: 38 μm) that had been subjected to release treatment using a comma coater, and then dried at 110° C. for 3 minutes to obtain an adhesive film having an adhesive layer having a thickness of about 20 μm.

(3) Manufacturing of semiconductor devices

: A wafer containing a semiconductor device, a bump chip (10.1 mm x 6.6 mm), was prepared, in which lead-free solder was formed to a height of 9 ㎛ on a copper pillar with a height of 10 ㎛ and a pitch of 40 ㎛.

After vacuum lamination at 50°C was performed so that the adhesive layer of the adhesive film was positioned on the bump surface of the wafer, each chip was individualized.

The individualized bump chips were thermocompression bonded to a 12.1 mm x 8.1 mm substrate chip having 40 ㎛ pitch connection pads using a thermocompression bonder. The conditions at that time were as follows: 100 N for 2 seconds at a head temperature of 120 ℃, and thermocompression bonding was performed at 200 N for 5 seconds while the head temperature was instantly increased to 260 ℃.

Weight (g) Example 1 Example 2 (a) KH-6021 102 102 (b) EOCN-104S 92 92 (c) KG-3038 300 300 (d) Manufacturing example 1 250 - Manufacturing example 2 - 250 Comparative manufacturing example 1 - - Comparative manufacturing example 2 - - SFP-120MC - - (e) DICY 5 5 2MA-OK 5 5

Weight (g) Comparative Example 1 Comparative Example 2 Comparative Example 3 (a) KH-6021 102 102 102 (b) EOCN-104S 92 92 92 (c) KG-3038 300 300 300 (d) Manufacturing example 1 - - - Manufacturing example 2 - - - Comparative manufacturing example 1 250 - - Comparative manufacturing example 2 - 250 - SFP-120MC - - 250 (e) DICY 5 5 5 2MA-OK 5 5 5

Weight (g) Reference Example 1 Reference example 2 Reference Example 3 (a) KH-6021 102 102 102 (b) EOCN-104S 92 92 92 (c) KG-3038 300 300 300 (d) Manufacturing example 1 150 150 50 Manufacturing example 2 - - - Comparative manufacturing example 1 - - - Comparative manufacturing example 2 - - - SFP-120MC - 100 200 (e) DICY 5 5 5 2MA-OK 5 5 5

In the above Tables 1 to 3, (a) phenol resin, (b) epoxy resin, (c) acrylic resin, (d) inorganic filler, (e) curing agent and curing accelerator, and the specific components are as follows.

*KH-6021: Bisphenol A novolac resin (DIC, softening point: about 125℃)

*EOCN-104S: Cresol novolac epoxy (equivalent weight: 180 g/eq, softening point: about 90 ℃)

*KG-3038: Acrylic acid ester polymer (Negami, 15 wt% glycidyl methacrylate repeating unit, glass transition temperature: 10 ℃)

*SFP-120MC: Silica (average particle size 300 nm, Denki Kagaku Kogyo)

*DICY: Hardener (dicyandiamide, TCI chemicals)

*2MA-OK: Curing accelerator (CUREZOL 2MAOK, EVONIK)

Exam example

The following tests were conducted on adhesive compositions, adhesive films, and semiconductor devices according to examples and comparative examples, respectively, and the results are shown in Tables 3 and 4 below.

(1) Peel strength of adhesive film on wafer

: The above adhesive films (width 18 mm, length 10 cm) were laminated to manufacture a multilayer adhesive film for dicing die bonding, and this was placed on a semiconductor chip having a thickness of 500 ㎛ and mounted on a hot plate.

Then, after exposing the dicing film - adhesive film - semiconductor chip composite at room temperature for about 3 hours, the peel strength (gf/inch) was measured at a temperature of 50°C to evaluate the adhesion of the semiconductor adhesive film to a silicon substrate.

(2) Hygroscopicity of adhesive film

: After laminating the above adhesive film to a thickness of 500 ㎛, a specimen was prepared by cutting it to a size of 5 cm X 5 cm. The weight (W ₀ ) of the specimen was measured.

The specimen was placed in a constant temperature and humidity oven at 85°C and 85% humidity, and after 24 hours, the weight (W ₁ ) of the specimen was measured.

The hygroscopicity was evaluated by calculating the change in weight (W ₀ , W ₁ ) of the above specimen as a percentage.

(3) Melting viscosity of adhesive film

: The adhesive film was laminated to a thickness of 320 ㎛ using a 60°C roll laminator, and then a specimen cut into a circle with a diameter of 8 mm was prepared.

Using TA's advanced rheometric expansion system (ARES), a shear rate of 5 rad/s and a heating rate of 10 ℃/min were applied, and the viscosity value (Pa.s) at 120 ℃, which is the bonding condition, was determined as the melt viscosity of the adhesive film.

(4) Evaluation of the challenge of adhesive films

: If the connection between the chip bumps of the semiconductor device is good, the conductivity is measured as zero (0). For the semiconductor device, the conductivity is measured a total of 5 times, and if it passes 4 or more times, it is evaluated as excellent (O), if it passes 2 to 3 times, it is evaluated as average (△), and if it passes 1 or less time, it is evaluated as poor (X).

(5) Evaluation of the connection status of semiconductor devices

: After polishing the cross-section of the semiconductor device to expose the connection, the exposed connection was observed using a scanning electron microscope.

SEM images taken with a scanning electron microscope are shown in FIG. 2 (E1: Example 1, E2: Example 2), FIG. 3 (C1: Comparative Example 1, C2: Comparative Example 2, C3: Comparative Example 3), and FIG. 4 (R1: Reference Example 1, R2: Reference Example 2, R3: Reference Example 3).

After observing the cross-sections of a total of 5 random points for the semiconductor device, if 4 or more points passed, it was evaluated as excellent (O), if 2 to 3 points passed, it was evaluated as average (△), and if 1 point or less passed, it was evaluated as defective (X) depending on whether cracks or poor connection between bumps occurred.

Example 1 Example 2 Peel strength (gf/inch) 45 43 Hygroscopicity (%) 4.5 4.8 Melt viscosity (Pa.s) 16500 15500 Challenge O O Connection status O O

Comparative Example 1 Comparative Example 2 Comparative Example 3 Peel strength (gf/inch) 64 70 36 Hygroscopicity (%) 5.0 5.8 4.0 Melt viscosity (Pa.s) 13300 17500 19000 Challenge △ X X Connection status X X X

Reference Example 1 Reference example 2 Reference Example 3 Peel strength (gf/inch) 60 45 41 Hygroscopicity (%) 5.0 4.8 4.2 Melt viscosity (Pa.s) 14500 14000 14300 Challenge O △ X Connection status △ X X

Referring to Tables 4 to 6 and FIGS. 2 to 4 above, it was confirmed that the adhesive compositions according to Examples 1 and 2 exhibit excellent adhesive strength during thermal compression bonding to semiconductor devices while minimizing the occurrence of resin traps.

Referring to Fig. 3, in the semiconductor devices according to Comparative Examples 1 and 2, it was confirmed that water contained in the silica particles evaporated and burst during bonding. In addition, in Comparative Example 3 including silica particles that were not surface-treated, it was confirmed that bonding between bumps did not occur.

Referring to Table 6 and Fig. 4 above, in the above Reference Example 1, an excessive pressing phenomenon was observed during bonding, and in the above Reference Examples 2 and 3, cracks were observed to occur in the bump bonding because the content of the surface-modified filler was relatively low.

1: Supporting materials
2: Adhesive layer
3: Protective film
4: Adhesive layer

Claims (12)

(a) 10 to 15 wt% of phenol resin;
(b) 10 to 15 wt% of epoxy resin;
(c) 25 to 40 wt% of (meth)acrylate resin, and
(d) 25 to 35 wt% of filler comprising inorganic particles surface-modified by a silane compound having a carboxylic acid terminal group;
An adhesive composition for a semiconductor package, comprising:
In paragraph 1,
An adhesive composition for a semiconductor package, wherein the (a) phenol resin is at least one compound selected from the group consisting of a bisphenol A novolac resin having a softening point of 105° C. or higher and a biphenyl novolac resin having a softening point of 105° C. or higher.
In paragraph 1,
The above (b) epoxy resin is at least one resin selected from the group consisting of bisphenol-based epoxy resin, biphenyl-based epoxy resin, naphthalene-based epoxy resin, fluorene-based epoxy resin, phenol novolac-based epoxy resin, cresol novolac-based epoxy resin, xyloc-based epoxy resin, trishydroxylphenylmethane-based epoxy resin, tetraphenylmethane-based epoxy resin, dicyclopentadiene-based epoxy resin, and dicyclopentadiene-modified phenol-based epoxy resin.
In paragraph 1,
An adhesive composition for a semiconductor package, wherein the (c) (meth)acrylate-based resin is a (meth)acrylic acid ester polymer containing 15 to 35 wt% of a (meth)acrylate-based repeating unit including an epoxy-based functional group.
In paragraph 1,
A filler including inorganic particles surface-modified by a silane compound having a carboxylic acid terminal group (d) above,
At least one inorganic particle selected from the group consisting of silica, zinc oxide, and zirconium oxide, and
Carboxylic acid terminal group bonded to the surface of the above inorganic particle via a silane compound
An adhesive composition for a semiconductor package, comprising:
In paragraph 5,
An adhesive composition for a semiconductor package, wherein the above-mentioned inorganic particles have an average particle diameter of 50 to 550 nm.
In paragraph 5,
An adhesive composition for a semiconductor package, wherein the above-mentioned inorganic particles have a moisture level of 10 to 80% according to the standard test method of DIN EN ISO 787-2.
In the first paragraph,
An adhesive composition for a semiconductor package, further comprising a curing agent and a curing catalyst.
In Article 8,
The above curing agent is at least one compound selected from the group consisting of amine compounds, acid anhydride compounds, amide compounds, and phenol compounds.
The above curing catalyst is at least one compound selected from the group consisting of a phosphorus compound, a boron compound, a phosphorus-boron compound, and an imidazole compound.
Adhesive composition for semiconductor packaging.
In the first paragraph,
The adhesive composition for the semiconductor package has a melt viscosity of 15,000 to 17,000 Pa.s measured at a temperature of 120° C.
delete An adhesive film comprising an adhesive composition for a semiconductor package according to claim 1.