KR20170131355A - Film-shaped adhesive composition, film-shaped adhesive, method of producing film-shaped adhesive, semiconductor package using film-shaped adhesive, and manufacturing method thereof - Google Patents

Abstract

A composition containing an epoxy resin, an epoxy resin curing agent, a phenoxy resin, and an aluminum nitride filler, wherein the content of the aluminum nitride filler is 30 to 60 volume% based on the total amount of the epoxy resin, epoxy resin curing agent, phenoxy resin and aluminum nitride filler %, And when the film adhesive obtained by the composition for film adhesive is heated at a temperature raising rate of 5 deg. C / minute at 25 deg. C, the minimum melt viscosity in a range of 200 to 10,000 Pa · s is reached at 80 deg. , A cured product having a thermal conductivity of 1.0 W / m · K after heat curing, and an electric conductivity of 50 μS / cm or less extracted water extracted into pure water at 121 ° C after heat curing at 20 hours, METHOD FOR PRODUCING FILM-ADHESIVE, SEMICONDUCTOR PACKAGE, AND METHOD FOR MANUFACTURING THE SAME

Description

Film-shaped adhesive composition, film-shaped adhesive, method of producing film-shaped adhesive, semiconductor package using film-shaped adhesive, and manufacturing method thereof

TECHNICAL FIELD The present invention relates to a composition for a film adhesive having a high thermal conductivity, a film adhesive, a method for producing a film adhesive, a semiconductor package using a film adhesive, and a method for producing the same.

2. Description of the Related Art In recent years, miniaturization and sophistication of electronic devices have progressed, and semiconductor packages to be mounted therein have been made more sophisticated, and semiconductor wafer wiring rules are becoming finer. As a result, heat is easily generated on the surface of the semiconductor element, so that there is a problem that the generated heat lowers, for example, the operating speed of the semiconductor element or causes malfunction of the electronic device.

In order to exclude adverse influences due to such heat, the constituent members of the semiconductor package are required to have thermal conductivity that relieves the generated heat to the outside of the package. In addition, a so-called die attach material which bonds between semiconductor elements and wiring boards or between semiconductor elements is required to have high thermal conductivity and sufficient insulating properties and adhesion reliability.

In addition, many of such die attach materials are conventionally used in paste form. However, in order to prevent contamination of other elements such as semiconductor elements and wire pads due to resin flow, resin blurring and the like, in recent years, in order to prevent film form (die As an adhesive film).

In order to achieve high heat conduction, it is necessary to call a high heat conductive filler. However, in general, when the filling amount of the filler is increased, the melt viscosity tends to rise. In the so-called die attach process in which the die attach film is attached to the back surface of the semiconductor wafer or the semiconductor element provided with the die attach film is mounted, The adherence between the die attach film and the adherend is temporarily reduced at the time of temporary mounting, and the air tends to be entrained at the interface between the die attach film and the adherend. This is based on that the surface of a semiconductor wafer, especially the surface of a wiring board on which semiconductor elements are mounted, is not necessarily in a smooth surface state. Here, the air entrained not only lowers the adhesive strength of the die attach film after heat curing but also causes package cracks. Therefore, in order to suppress the rise in melt viscosity, it is necessary to lower the charge amount as much as possible, to achieve high thermal conductivity, and to select a filler having higher thermal conductivity.

In the manufacturing process of the semiconductor package, it is also necessary that the abrasion rate of the processing blade by the die attach film is small in the so-called dicing step in which the die attach film and the semiconductor wafer formed with the semiconductor element are simultaneously cut. When the high thermal conductive filler having a high hardness is selected, the abrasion rate of the processing blade by the die attach film is increased, and predetermined cutting is possible for a while after the start of the cutting step (dicing step). However, It becomes insufficient. If the frequency of replacement of the blades is increased in order to prevent this problem from occurring, productivity is lowered, leading to cost increase. On the other hand, when a blade having a small amount of wear is used, chipping or the like The yield is lowered.

In recent years, a copper material has been used for a semiconductor member. For example, a copper wire is used as a metal wire rather than a gold material conventionally used in order to reduce the cost of assembling a semiconductor package. Further, in order to improve the processing capability of semiconductor devices, a copper material having a lower electrical resistance than aluminum materials conventionally used is used as a semiconductor device circuit material. However, when the die attach film is adhered to such a semiconductor member made of copper, it is necessary that the semiconductor package is not corroded during a reliability test such as bias high stress test (HAST) under high temperature and high humidity. For this reason, it is necessary to use a small amount of ionic impurities as the die attach film.

As described above, the high thermal conductive diatomaceous film has the following characteristics: i) low melt viscosity to exhibit adhesion, ii) abrasion resistance of the inner blade in the dicing step, and iii) low ionic impurity property for not corroding the copper- .

As a material that can be used as a high thermal conductive diatomaceous film, for example, Patent Document 1 discloses an epoxy resin, a polymer component having a glass transition temperature of at least 95 캜, a polymer component having a glass transition temperature of -30 캜 or lower, A high thermal conductive adhesive sheet composed of an inorganic filler of K or more has been proposed. However, in the sheet for high thermal conductive adhesion described in Patent Document 1, aluminum oxide having high hardness and thermal conductivity and low melt viscosity are used, and it can be assumed that the problem of abrasion resistance of the inner blade remains, and The examination of ionic impurities was also insufficient.

Further, in Patent Document 2, an epoxy resin having high thermal conductivity particles, a mesogen, and a high thermal conductivity resin composition containing a high molecular weight component have been proposed. However, in the high thermal conductive resin composition described in Patent Document 2, aluminum oxide having a high degree of thermal conductivity and adhesiveness is used, and it is presumed that the problem of abrasion resistance of the inner blade remains. Further, Reviews were also inadequate.

Further, in Patent Document 3, a sheet of a heat conductive member made of a thermally conductive filler made of aluminum hydroxide and silicon dioxide and a silicone resin has been proposed. However, although the sheet of the heat conduction member described in Patent Document 3 has a somewhat high thermal conductivity, the adhesion with an adherend still has a problem, and examination of ionic impurities is also insufficient.

Japanese Patent Publication No. 5541613 Japanese Laid-Open Patent Publication No. 2013-6893 Japanese Patent Application Laid-Open No. 2009-286809

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for manufacturing a copper-clad semiconductor element which is excellent in adhesion with an adherend, A film-shaped adhesive, a method of producing a film-shaped adhesive, a method of producing a film-shaped adhesive, a semiconductor package using the film-shaped adhesive, and a method of manufacturing the film-shaped adhesive, which can obtain a film-shaped adhesive exhibiting excellent thermal conductivity after thermal curing .

Means for Solving the Problems The present inventors have conducted diligent studies in order to achieve the above object, and as a result, it has been found that the present invention is achieved by the following constitutions.

(1) A composition for film adhesive comprising an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C) and an aluminum nitride filler (D)

Wherein the content of the aluminum nitride filler (D) is 30 to 60% by volume based on the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) Lt;

When the film adhesive obtained by the composition for film adhesive is heated at a temperature raising rate of 5 deg. C / minute at 25 deg. C, it reaches the lowest melt viscosity in the range of 200 to 10,000 Pa · s at 80 deg. C or higher, And the electric conductivity of the extracted water extracted into pure water at 121 占 폚 for 20 hours after curing is 50 占 / / cm or less.

(2) The aluminum nitride filler (D) has a surface oxidation layer on the surface of the filler (1), characterized in that a water-repellent surface treatment with a phosphoric acid or a phosphoric acid compound is carried out.

(3) Further, an ion trap agent selected from a triazine thiol compound, a zirconium compound, an antimony bismuth compound and a magnesium aluminum compound is contained in an amount of 1.0 to 3.0% by mass based on the aluminum nitride filler (D) (1) or (2).

(4) A film-form adhesive obtained by the composition for a film-form adhesive according to any one of (1) to (3) above.

(5) A method for producing a film-shaped adhesive, which comprises coating the film-shaped adhesive composition described in any one of (1) to (3) above onto a release-treated base film and drying.

(6) a first step of thermally pressing the film-shaped adhesive agent and the dicing tape described in (4) on the back surface of a semiconductor wafer having at least one semiconductor circuit formed on the surface thereof to form an adhesive layer,

A second step of dicing the semiconductor wafer and the adhesive layer at the same time to obtain a semiconductor chip with the adhesive layer including the semiconductor wafer and the adhesive layer,

A third step of releasing the dicing tape from the adhesive layer and thermally bonding the adhesive layer to the semiconductor chip and the wiring substrate via the adhesive layer,

And a fourth step of thermally curing the adhesive layer.

(7) A semiconductor package obtained by the manufacturing method according to (6) above.

According to the present invention, it is possible to maintain a low ionic impurity property so as not to corrode a copper material semiconductor member and to have excellent adhesion with an adherend, a sufficiently low abrasion rate of a processing blade, It is possible to provide a composition for a film-form adhesive capable of obtaining a conductive film-like adhesive, a film-form adhesive, a method for producing a film-form adhesive, a semiconductor package using the film-form adhesive, and a method for producing the same.

These and other features and advantages of the present invention will become more apparent from the following description, with reference to the accompanying drawings appropriately.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic vertical sectional view showing a preferred embodiment of a first step of the method for manufacturing a semiconductor package of the present invention. FIG.
Fig. 2 is a schematic longitudinal sectional view showing a preferred embodiment of the second step of the method of manufacturing the semiconductor package of the present invention. Fig.
3 is a schematic vertical sectional view showing a preferred embodiment of the third step of the method of manufacturing the semiconductor package of the present invention.
4 is a schematic longitudinal sectional view showing a preferred embodiment of a process for connecting a bonding wire in the method for manufacturing a semiconductor package of the present invention.
5 is a schematic longitudinal sectional view showing an example of a multi-layer stacked embodiment of the method of manufacturing the semiconductor package of the present invention.
6 is a schematic longitudinal sectional view showing another multi-layer stacked embodiment of the method of manufacturing the semiconductor package of the present invention.
7 is a schematic longitudinal sectional view showing a preferred embodiment of a semiconductor package manufactured by the method for manufacturing a semiconductor package of the present invention.

<< Composition for film-form adhesive >>

The epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the aluminum nitride filler (D) are used as the composition for a film adhesive of the present invention (hereinafter referred to as a composition for a high thermal conductive film- And the content of the aluminum nitride filler (D) is in the range of 30 to 50 parts based on the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the aluminum nitride filler (D) 60 vol%.

The high thermal conductive film adhesive obtained by the composition for a high thermal conductive film adhesive of the present invention preferably has a thermal conductivity in the range of 200 to 10,000 Pa · s at a temperature of 80 ° C or higher when it is heated at a temperature raising rate of 5 ° C / The electric conductivity of the extracted water extracted into pure water at 121 占 폚 for 20 hours after the thermal curing is reached is 50 占 / / cm or less after reaching the lowest melt viscosity, giving a cured product with a thermal conductivity of 1.0 W / m 占 이상의 or more after heat curing.

Here, after thermal curing in the measurement of the thermal conductivity, the electric conductivity of the extracted water, and the ammonium ion concentration, it means after heating at 180 ° C for one hour.

&Lt; Properties of film-like adhesive >

The lowest melt viscosity of the high thermal conductive film-like adhesive obtained by the composition for a high thermal conductive film adhesive of the present invention is preferably in the range of 200 to 10,000 Pa · s at 80 ° C or higher when the temperature is raised at a temperature raising rate of 5 ° C / Lt; / RTI &gt; The lowest melt viscosity is preferably in the range of 200 to 3000 Pa · s, more preferably 200 to 2000 Pa · s. When the melt viscosity is higher than this range, voids are likely to remain between the wiring board concavo-convex portions when the semiconductor chip provided with the film-form adhesive is thermally bonded onto the wiring board. When the thickness is smaller than this range, the film-like adhesive tends to be punched out when the semiconductor chip provided with the film-form adhesive is mounted on the wiring board. In the present invention, the melt viscosity is measured using a rheometer (product name: RS6000, manufactured by Haake), the change in viscosity resistance at a temperature range of 25 to 200 DEG C and a temperature increase rate of 5 DEG C / min is measured, - Viscosity resistance when the temperature is above 80 ℃ in the viscous resistance curve.

In order to set the minimum melt viscosity to the above-mentioned range, the content of the aluminum nitride filler (D) and the kind of the aluminum nitride filler (D), or the amount of the coexisting compound such as epoxy resin (A) It can be adjusted depending on the kind and content of these.

The high thermal conductive film adhesive of the present invention has a thermal conductivity of 1.0 W / m · K or more after heat curing. The thermal conductivity is preferably 1.5 W / m · K or more. If the thermal conductivity is less than the lower limit, the generated heat tends to be difficult to relief to the outside of the package. The high thermal conductive film adhesive of the present invention can be obtained by bringing the high thermal conductive film adhesive of the present invention into contact with an adherend such as a semiconductor wafer or a wiring board and thermally curing the adhesive in order to exhibit such excellent thermal conductivity after heat curing, The heat radiation efficiency to the outside is improved.

The upper limit of the thermal conductivity is not particularly limited, but is practically 5.0 W / m · K or less.

In the present invention, the thermal conductivity of the film-shaped adhesive after the heat curing is measured by a heat flow method (JIS-110, manufactured by EKO Instruments) A1412). The term &quot; heat conductivity &quot;

In order to set the thermal conductivity to the above-described range, it is preferable that the content of the aluminum nitride filler (D) and the kind of the aluminum nitride filler (D), the kind of the compound or resin coexisting such as the epoxy resin (A) It can be adjusted by the content of these.

Further, in the high thermal conductive film adhesive of the present invention, the electric conductivity of extracted water extracted into pure water at 121 占 폚 for 20 hours after heat curing is 50 占 / / cm or less. The electric conductivity is preferably 40 mu S / cm or less. When the electrical conductivity exceeds the upper limit, the copper material is easily corroded in a reliability test such as bias HAST under high temperature and high humidity of the semiconductor package.

The lower limit of the electric conductivity is not particularly limited, but is practically 0.1 mu S / cm or more.

In the present invention, the electrical conductivity is measured by measuring the electrical conductivity of the extracted water obtained by putting the film-shaped adhesive after thermosetting into purified water at 121 ° C for 20 hours, using an electric conductivity meter (trade name: AE-200, (Manufactured by Mettler-Toledo International Inc.).

In order to set the electric conductivity to the above-mentioned range, it is possible to adjust the surface-modified aluminum nitride filler (D) and phosphate ester surfactant or ion trap agent (ion trap agent) as an additive.

&Lt; Epoxy resin (A) >

The epoxy resin (A) contained in the composition for a high thermal conductive film-like adhesive of the present invention may be any one of liquid, solid or semi-solid. In the present invention, the liquid refers to a softening point of less than 50 占 폚. The solid refers to a softening point of 60 占 폚 or higher. The semi-solid has a softening point between the softening point of the liquid and the softening point of the solid Lt; 0 &gt; C). As the epoxy resin (A) used in the present invention, from the viewpoint of obtaining a film-form adhesive capable of reaching a low melt viscosity in a suitable temperature range (for example, 60 to 120 ° C), the epoxy resin desirable. Further, in the present invention, the softening point is a value measured by a softening point test (ring ball method) (measurement conditions: according to JIS-2817).

In the epoxy resin (A) used in the present invention, the cross-linking density of the cured body is increased, and consequently, the contact probability of the aluminum nitride filler (D) to be blended is high and the contact area is widened to obtain a higher thermal conductivity From the viewpoint, the epoxy equivalent is preferably 500 g / eq or less, more preferably 150 to 450 g / eq. In the present invention, the epoxy equivalents refer to grams (g / eq) of the resin containing one gram equivalent of an epoxy group.

Examples of the skeleton of the epoxy resin (A) include phenol novolak type, orthocresol novolac type, cresol novolac type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalene diol type, Triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, trimethylol methane type and the like. Among them, triphenylmethane type, bisphenol A type, cresol novolak type, and oscocresol novolac type are preferable from the viewpoint of obtaining a film-like adhesive having a low crystallinity of resin and good appearance.

The content of the epoxy resin (A) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, based on the total mass of the composition for a high thermal conductive film adhesive of the present invention. If the content is less than the above lower limit, the resin component having a high crosslinking density at the time of curing tends to be reduced, so that the thermal conductivity of the film adhesive tends to be hard to be improved. On the other hand, The film state (film tackiness or the like) tends to change even at a temperature change.

&Lt; Epoxy resin curing agent (B) >

As the epoxy resin curing agent (B) contained in the composition for a high thermal conductive film adhesive of the present invention, known curing agents such as amines, acid anhydrides and polyhydric phenols can be used. In the present invention, it is preferable that the epoxy resin (A) and the phenoxy resin (C) have a low melt viscosity, exhibit hardenability at a high temperature exceeding a certain temperature, exhibit fast curability, It is preferable to use a latent curing agent from the viewpoint that a composition for a film-form adhesive having a high storage stability as far as possible is obtained.

Examples of the latent curing agent include dicyandiamides, imidazoles, curing catalyst complex type polyhydric phenols, hydrazides, boron trifluoride-amine complexes, amine imides, polyamine salts, and modifications thereof or microcapsule type . In the present invention, from the viewpoint that the water absorptivity after heat curing is low and the elastic modulus after heat curing is low, it is difficult to cause peeling failure in the moisture absorption reflow test after assembling the semiconductor package, More preferable.

Examples of the curing catalyst complex-type polyhydric phenols include novolak type phenol resins, phenol aralkyl type phenol resins, polyvinyl type phenol resins and resorcinol type phenol resins.

These may be used singly or in combination of two or more kinds.

The content of the epoxy resin curing agent (B) is preferably 0.5 to 100 mass%, more preferably 1 to 80 mass%, with respect to the epoxy resin (A). If the content is less than the lower limit described above, the curing time tends to be longer. On the other hand, if the content exceeds the upper limit, the excess curing agent remains in the film adhesive and the remaining curing agent adsorbs moisture. There is a tendency that defects tend to occur in the test.

&Lt; Phenoxy resin (C) >

The phenoxy resin (C) contained in the composition for a high thermal conductive film adhesive of the present invention is used for imparting sufficient adhesiveness and film formability (film formability) to the film forming layer. The phenoxy resin has good compatibility with the epoxy resin, and has low melt viscosity and good adhesiveness. The phenoxy resin is obtained from bisphenol such as bisphenol A and epichlorohydrin. In the present invention, a thermoplastic resin having a mass average molecular weight of 10,000 or more is preferable. By blending a phenoxy resin, it is effective in eliminating tackiness at room temperature, fragility (vulnerability), and the like. Preferred examples of the phenoxy resin include bisphenol A type, bisphenol A / F type, bisphenol F type, and cardo-skeleton type phenoxy resins. The phenoxy resin is preferably a phenoxy resin obtained by copolymerization of 1256 (trade name: bisphenol A type phenoxy resin, manufactured by Mitsubishi Kagaku Kabushiki Kaisha), YP-70 (trade name: bisphenol A / F type phenoxy resin, (Manufactured by Shin-Nihon Epoxy KK), FX-316 (trade name: bisphenol F type phenoxy resin, Shin-Nika Epoxy Seiko Co., Ltd.), and FX-280S A commercially available phenoxy resin such as skeleton-type phenoxy resin, Shin-Nikka Epoxy Seijo Co., Ltd.) may be used.

Here, the mass average molecular weight is a value determined by GPC (Gel Permeation Chromatography) in terms of polystyrene.

The glass transition temperature (Tg) of the phenoxy resin is preferably less than 100 占 폚, and more preferably less than 80 占 폚.

The lower limit of the glass transition temperature (Tg) is preferably 0 deg. C or higher, more preferably 10 deg. C or higher.

The content of the phenoxy resin is preferably from 1 to 20 mass%, more preferably from 3 to 15 mass%, and even more preferably from 4 to 13 mass%, based on the epoxy resin (A). When the content is in this range, the film state is good (film tackiness is reduced), and film fragility can be suppressed.

&Lt; Aluminum nitride filler (D) >

The aluminum nitride filler (D) contained in the composition for a high thermal conductive film-like adhesive of the present invention contributes to high thermal conductivity and reduction of linear expansion coefficient of the film adhesive. If the value of the coefficient of linear expansion is high, the difference in coefficient of linear expansion with respect to the wiring substrate becomes large, so that the effect of suppressing the stress with these adhered materials is low and this is not preferable because it leads to generation of package cracks.

In general, since aluminum nitride has a low affinity with the resin, the thermal resistance at the interface with the resin tends to increase. Further, since the reactivity with water is high, the surface is hydrolyzed by contact with water in the powder state, and ammonia is easily generated. This ammonia becomes ammonium ion, and copper material is easily corroded in a reliability test such as bias HAST under high temperature and high humidity of a semiconductor package. Therefore, in the present invention, the aluminum nitride filler (D) is preferably surface-modified. As a method for modifying the surface of aluminum nitride, it is preferable to provide an oxide layer of aluminum oxide on the surface layer to improve the water resistance and to improve the affinity with the resin by surface treatment with phosphoric acid or a phosphate compound.

The phosphoric acid used in the surface treatment is selected from the group consisting of orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ O ₇ ), metaphosphoric acid ((HPO ₃ ) n, n being an integer representing the degree of condensation) . Examples of the phosphoric acid compound include organic phosphoric acid such as alkylphosphonic acid, arylphosphonic acid, alkylphosphoric acid and arylphosphoric acid (for example, methylphosphonic acid, ethylphosphonic acid, hexylphosphonic acid, vinylphosphonic acid, phenylphosphonic acid, Phosphoric acid, hexyl phosphoric acid).

It is also preferable to surface-treat the surface of the aluminum nitride particles with a silane coupling agent.

It is also preferable to use an ion trap agent (ion trap agent) in combination.

In the present invention, the content of the aluminum nitride filler (D) is preferably in the range of 30 to 50 parts by weight based on the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) 60% by volume, more preferably 35% by volume to 50% by volume. This is because the lowest melt viscosity value is controlled by the aluminum nitride filler amount. If the compounding amount is larger than the range, the minimum melt viscosity value becomes large, and when the semiconductor chip provided with the present film-shaped adhesive is thermocompression bonded onto the wiring substrate, the gap tends to remain between the wiring substrate gaps and the film fragility becomes strong. When the blending amount is less than the range, the minimum melt viscosity value becomes small, and when the semiconductor chip provided with the present film-like adhesive is mounted on the wiring board, the film-like adhesive tends to be easily peeled off.

In the present invention, the aluminum nitride filler (D) is preferably spherical from the viewpoint of high solubility and fluidity. The average particle diameter is preferably 0.01 to 5 mu m. If the particle diameter is less than 0.01 mu m, the filler tends to be aggregated, resulting in unevenness in the production of the film, and the uniformity of the film thickness of the obtained adhesive film may be deteriorated. When the particle size is larger than 5 mu m, when the thin film is produced by a coating machine such as a roll knife coater, the filler is synchronized and streaks easily occur on the film surface.

The aluminum nitride (D) used in the present invention preferably has a Mohs hardness of 7 to 8. When the Mohs hardness exceeds the upper limit, the abrasion rate of the processing blade by the film-shaped adhesive increases. In the present invention, the Mohs hardness is measured by a 10-stage Mohs hardness meter, and the hardness of the measurement object is visually measured by scratching the measurement object with small hardness minerals in order and judging whether the measurement object is scratched or not. It refers to one value.

In the present invention, the average particle diameter refers to the particle diameter when 50% of the total volume of the particles is assumed to be 100% in the particle size distribution. The particle diameter is determined by the laser diffraction / scattering method (measuring conditions: Sodium, laser wavelength: 780 nm, measurement apparatus: microtrack MT3300EX). Further, in the present invention, the spherical form means a true or substantially rounded, substantially spherical form.

Examples of the method of compounding the aluminum nitride filler (D) with a resin binder include a method of directly blending a powdery aluminum nitride filler with a silane coupling agent, a phosphoric acid or a phosphoric acid compound or a surfactant in accordance with necessity (integral blend method) A slurry-form aluminum nitride filler in which an aluminum nitride filler treated with a surface treating agent such as a silane coupling agent, phosphoric acid or a phosphoric acid compound or a surfactant is dispersed in an organic solvent can be used. Particularly, in the case of producing a thin film, it is more preferable to use a slurry aluminum nitride filler. This is achieved by mixing a resin component such as an epoxy resin, an epoxy resin curing agent and a polymer into a dispersion of a surface-treated aluminum nitride filler dispersed in a smaller organic solvent so that even an aluminum nitride filler having a small particle size can be uniformly This is because the surface appearance of the obtained film-like adhesive becomes good.

The silane coupling agent is one in which at least one hydrolyzable group such as an alkoxy group and an aryloxy group is bonded to a silicon atom, and in addition, an alkyl group, an alkenyl group or an aryl group may be bonded. The alkyl group is preferably an amino group, an alkoxy group, an epoxy group, or a (meth) acryloyloxy group substituted with an amino group (preferably a phenylamino group), an alkoxy group (preferably a glycidyloxy group) It is more preferable that the iodine group is substituted.

The silane coupling agent includes, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxy silane, phenyl triethoxy silane, N- phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane in one oxy methyl dimethoxysilane, one oxy-trimethoxysilane, 3-meth 3-methacrylate to an oxy-propyltriethoxysilane in an oxy-propyl methyl diethoxy silane, 3-methacryloxypropyltrimethoxysilane as a silane methacrylate, and the like.

The surfactant may be either anionic, cationic or nonionic, and may be a polymeric compound.

In the present invention, an anionic surfactant is preferable, and a phosphate ester surfactant is more preferable.

As the phosphate ester surfactant, a phosphate ester represented by the following general formula (1) is preferable.

In the general formula (1), R ¹ represents an alkyl group, an alkenyl group or an aryl group, L ¹ represents an alkylene group, m represents an integer of 0 to 20, and n represents 1 or 2.

The number of carbon atoms of the alkyl group in R ¹ is preferably from 1 to 20, more preferably from 8 to 20, still more preferably from 8 to 18, and examples thereof include butyl, pentyl, hexyl, heptyl, Hexyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl. Of these, decyl, undecyl and dodecyl are preferable, and undecyl is particularly preferable.

The carbon number of the alkenyl group in R ¹ is preferably from 2 to 20, more preferably from 8 to 20, still more preferably from 8 to 18, and examples thereof include allyl and oleyl.

The carbon number of the aryl group in R ¹ is preferably from 6 to 20, more preferably from 6 to 20, still more preferably from 6 to 18, and examples thereof include phenyl and nonylphenyl.

The number of carbon atoms of the alkyl group in L ¹ is preferably 2 or 3, more preferably 2, and examples thereof include ethylene and propylene.

m is preferably an integer of 0 to 10.

The phosphoric acid ester represented by the general formula (1) may be a mixture of n and 1.

The phosphoric acid ester represented by the general formula (1) may be those commercially available as a phosphapol series manufactured by Toho Chemical Industry Co., Ltd. For example, phosphopols RS-410, 610, 710, phosphanol RL-310, phosphanol RA-600, phosphanol ML-200, 220, 240 and phosphanol GF-199 (all trade names).

The silane coupling agent and the surfactant are preferably contained in an amount of 0.1 to 5.0 mass% with respect to the aluminum nitride filler (D).

If the content of the silane coupling agent or the surfactant is less than the above lower limit, the aluminum nitride filler (D) tends to aggregate and the appearance of the film surface deteriorates. On the other hand, if the upper limit is above the upper limit, excess silane coupling agent and surfactant remaining in the system are volatilized in the semiconductor assembly heating process (for example, reflow process), causing peeling at the bonding interface.

<Other additives>

The composition for a film adhesive of the present invention is not limited to the above epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the aluminum nitride filler (D) It may further contain an additive such as an ion trap agent (ion trap agent), a curing catalyst, a viscosity adjusting agent, an antioxidant, a flame retardant, a colorant, a stress relieving agent such as butadiene rubber or silicone rubber.

Of these, in particular, it is preferable to use an ion trap agent for the purpose of replenishing ammonium ions generated by hydrolysis of aluminum nitride with water. Examples of the ion trap agent include an inorganic ion trap agent including a triazinethiol compound, a zirconium compound, an antimony bismuth compound, and a magnesium aluminum compound.

It is more preferable that the ion trap agent is used in an amount of 1.0 to 3.0 mass% with respect to the aluminum nitride filler (D).

If the content of the ion trap agent is less than the lower limit described above, the generated ammonium ions remain in the system and corrosion of the circuit member tends to occur during the reliability test. On the other hand, when the upper limit is exceeded, the excess ion trap material remaining in the system is absorbed, and the adhesive strength of the adhesive interface tends to be lowered, which causes peeling in the reliability test.

In the present invention, the concentration of the ammonium ion is preferably 80 ppm or less, and more preferably 70 ppm or less, under the measurement conditions of the discharged water conductivity.

If the ammonium ion concentration exceeds the upper limit, ammonium ion or other ion impurity concentration increases, and corrosion of the circuit member tends to occur in the reliability test.

In the present invention, it is also preferable to use a curing catalyst. As the curing catalyst, an in-borocyte curing catalyst, a triphenylphosphine type curing catalyst, an imidazole type curing catalyst and an amine type curing catalyst can be mentioned, and a phosphorus-boron curing catalyst and a triphenylphosphine type curing catalyst are preferable, An in-borocyte curing catalyst is particularly preferred.

As the triphenylphosphine type curing catalyst, for example, triarylphosphines such as triphenylphosphine and tri-p-tolylphosphine are preferable.

As the phosphorus-containing curing catalyst, tetraphenylphosphonium tetraphenylborate (trade name: TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name: TPP-MK), triphenylphosphine triphenylborane ; TPP-S) and the like (all available from Hokokagaku Kogyo Kogyo Co., Ltd.). Of these, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetra-p-triborate are preferable from the standpoint of good storage stability at room temperature because of their excellent latency.

The curing catalyst is preferably contained in an amount of 0.1 to 5.0 mass% with respect to the epoxy resin curing agent (B).

&Lt; Film-shaped adhesive &gt;

As a preferred embodiment of the method for producing a film-form adhesive of the present invention, there is a method of applying the composition for a high thermal conductive film-form adhesive of the present invention onto one side of a release-treated base film, followed by heating and drying However, this method is not particularly limited. The base film subjected to the release treatment may be any film as long as it can function as a cover film of the resulting film-like adhesive, and any known film can be suitably employed. Examples thereof include polypropylene (PP) subjected to release treatment, polyethylene (PE) subjected to release treatment, and polyethylene terephthalate (PET) subjected to release treatment. As a coating method, a known method can be suitably employed, and examples thereof include a method using a roll knife coater, a gravure coater, a die coater, a reverse coater, and the like.

The film-like adhesive of the present invention thus obtained preferably has a thickness of 5 to 200 占 퐉 and more preferably 5 to 40 占 퐉 from the viewpoint that the wiring substrate and the surface of the semiconductor chip can be sufficiently filled with irregularities. If the thickness is less than the lower limit described above, the wiring substrate and the irregularities on the surface of the semiconductor chip can not be sufficiently filled and sufficient adhesion can not be ensured. On the other hand, if the upper limit is exceeded, , The amount of residual solvent is increased and the film tackiness tends to become strong.

<< Semiconductor Package and Method for Manufacturing the Same >>

Next, preferred embodiments of the semiconductor package and the manufacturing method thereof of the present invention will be described in detail with reference to the drawings. In the following description and drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted. Figs. 1 to 7 are schematic longitudinal sectional views showing one preferred embodiment of each step of the method for manufacturing a semiconductor package of the present invention.

In the method of manufacturing a semiconductor package of the present invention, first, as shown in Fig. 1, as a first step, on the back surface of a semiconductor wafer 1 having at least one semiconductor circuit formed on its surface, The adhesive layer is thermally pressed to provide the adhesive layer 2 and then the semiconductor wafer 1 and the dicing tape 3 are provided with the adhesive layer 2 interposed therebetween. At this time, the product in which the adhesive layer 2 and the dicing tape 3 are integrated may be thermocompressed at one time. As the semiconductor wafer 1, a semiconductor wafer having at least one semiconductor circuit formed on the surface thereof can be suitably used, and examples thereof include a silicon wafer, a SiC wafer, and a GaS wafer. As the adhesive layer 2, the high thermal conductive film adhesive of the present invention may be used singly as a single layer or as a laminate of two or more layers. As a method of providing the adhesive layer 2 on the back surface of the wafer 1, a method capable of stacking the film adhesive on the back surface of the semiconductor wafer 1 can be suitably employed, In the case of laminating two or more layers after the film-like adhesive is laminated on the back surface, a method in which a film-like adhesive is laminated sequentially until a desired thickness is obtained, or a method in which a film- A method of sticking to the back surface of the wafer 1, and the like. A device used when the adhesive layer 2 is provided on the back surface of the semiconductor wafer 1 is not particularly limited and known devices such as a roll laminator and a manual laminator can be suitably used, for example.

Next, as a second step, as shown in Fig. 2, the semiconductor wafer 1 and the adhesive layer 2 are diced at the same time to form the adhesive layer 2 having the semiconductor wafer 1 and the adhesive layer 2 And the semiconductor chip 5 is obtained. The dicing tape 3 is not particularly limited, and a dicing tape appropriately known can be used. The apparatus used for dicing is not particularly limited, and a dicing apparatus suitably known can be used.

3, the dicing tape 3 is removed from the adhesive layer 2 and the adhesive layer is applied to the adhesive layer 2 (the semiconductor chip 5 and the wiring board 6) And the semiconductor chip 4 is mounted on the wiring board 6 with the adhesive layer. As the wiring board 6, a board on which a semiconductor circuit is formed on the surface can be suitably used. For example, a printed circuit board (PCB), various lead frames, and electronic parts such as resistors and capacitors are mounted on the surface of the board .

The method of mounting the semiconductor chip 5 on the wiring board 6 is not particularly limited and the adhesive layer may be formed by using the adhesive layer 2 so that the semiconductor chip 5 is bonded to the wiring board 6, It is possible to appropriately employ a conventional method capable of bonding the electronic component mounted on the surface of the substrate 6 to the electronic component. Examples of such a mounting method include a conventional method using a mounting technique using a flip chip bonder having a heating function from above, a method using a die bonder having a heating function only from the bottom, a method using a laminator, .

As described above, by mounting the semiconductor chip 5 on the wiring board 6 via the adhesive layer 2 made of the film-like adhesive of the present invention, it is possible to mount the semiconductor chip 5 on the wiring board 6 The film type adhesive can follow the unevenness, so that it becomes possible to fix the semiconductor chip 4 and the wiring board 6 in close contact with each other.

Next, as the fourth step, the film-shaped adhesive of the present invention is thermally cured. The temperature of the thermosetting is not particularly limited as long as it is not lower than the thermosetting initiation temperature of the film-form adhesive of the present invention and varies depending on the kind of the resin to be used and can not be collectively stated. For example, Deg.] C, and more preferably 140 to 180 [deg.] C from the viewpoint that curing at a higher temperature can be cured in a short time. If the temperature is lower than the thermosetting initiation temperature, the thermosetting does not proceed sufficiently and the strength of the adhesive layer 2 tends to decrease. On the other hand, if the upper limit is exceeded, the epoxy resin, the curing agent, Etc. are volatilized and tend to foam easily. The time for the curing treatment is preferably 10 to 120 minutes, for example. In the present invention, by thermally curing the film-form adhesive at a high temperature, it is possible to obtain a semiconductor package in which the wiring board 6 and the semiconductor chip 4 are firmly bonded to each other without generating voids even when curing at a high temperature .

Next, in the method of manufacturing a semiconductor package of the present invention, it is preferable that the wiring board 6 and the adhesive layer portion are connected to each other via the bonding wire 7, as shown in Fig. The connection method is not particularly limited, and conventionally known methods such as a wire bonding method, a TAB (Tape Automated Bonding) method, and the like can be suitably employed.

Alternatively, a plurality of semiconductor chips 4 may be stacked on the surface of the mounted semiconductor chip 4 by thermocompression bonding and thermosetting the other semiconductor chip 4 and then connecting them to the wiring board 6 by wire bonding. For example, as shown in Fig. 5, there is a method in which semiconductor chips are shifted and laminated, or a method in which the bonding wire 7 is laminated while thickening the second adhesive layer 2 as shown in Fig. 6 .

In the method for manufacturing a semiconductor package of the present invention, it is preferable that the wiring board 6 and the adhesive layer portion seal the semiconductor chip 5 with the sealing resin 8 as shown in Fig. 7, (9) can be obtained. The sealing resin 8 is not particularly limited, and any well-known sealing resin which can be used for manufacturing a semiconductor package can be used. Also, the sealing method using the sealing resin 8 is not particularly limited, and a well-known method can be adopted.

According to the method for manufacturing a semiconductor package of the present invention, it is possible to provide an adhesive layer (2) which is excellent in adhesion to an adherend, has a sufficiently low abrasion rate of a processing blade, and does not corrode a copper material semiconductor material. In addition, by exerting excellent thermal conductivity after heat curing, it is possible to efficiently relieve the heat generated from the surface of the semiconductor chip 4 to the outside of the semiconductor package 9.

[Example]

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. In each of the Examples and Comparative Examples, the melt viscosity, the thermal conductivity, the extracted water electrical conductivity, the blade wear rate, and the corrosion resistance were evaluated by the methods shown below.

(Measurement of Minimum Melt Viscosity)

The film-like adhesives obtained in each of the Examples and Comparative Examples were cut into a size of 5.0 cm x 5.0 cm and laminated. A test piece having a thickness of about 1.0 mm was obtained by sticking on a hot plate at a stage of 70 DEG C with a hand roller. The test piece was measured for the change in the viscosity resistance at a temperature range of 20 to 250 ° C and a temperature rise rate of 5 ° C / min using a rheometer [RS6000, manufactured by Haake Co., Ltd.], and the lowest melt viscosity (Pa · s) was calculated.

(Evaluation of void)

The film-like adhesive obtained in each of the examples and the comparative examples was first dipped at a temperature of 70 DEG C and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, manufactured by TECHNO VISION, INC. Was adhered to one surface of a glass substrate (10 占 10 cm, thickness 50 占 퐉) serving as a silicon wafer, and then the above-mentioned manual laminator was attached to the glass substrate as a dummy silicon wafer at the room temperature and at a pressure of 0.3 MPa Dicing tape [trade name: K-13, manufactured by Furukawa Electric Kogyo Co., Ltd.] and a dicing frame [trade name: DTF2-8-1H001, manufactured by DISCO Co., Ltd.] were adhered on the surface of the substrate. Next, a dicing machine (trade name: DFD-6340, manufactured by DISCO) equipped with a biaxial dicing blade [Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO / Z2: NBC-ZH127F- To obtain a size of 10 mm x 10 mm, thereby obtaining a glass chip as a dummy semiconductor chip.

Next, under the conditions of a temperature of 120 占 폚, a pressure of 0.1 MPa (load: 1000 gf) and a time of 1.0 second with a die bonder (trade name: DB-800 manufactured by Hitachi High-Technologies Corporation) Was thermocompression-bonded onto a wiring board (FR-4 substrate, thickness 200 μm). The state of the film-shaped adhesive after thermocompression bonding was observed from the back surface of the glass substrate. The void evaluation was evaluated according to the following evaluation criteria.

[Evaluation standard]

A: void free

C: void has occurred

(Thermal conductivity)

The obtained film-form adhesive was cut into square pieces of 50 mm or more on one side and the cut samples were stacked so as to have a thickness of 5 mm or more and placed on a disc mold having a diameter of 50 mm and a thickness of 5 mm. Deg.] C and a pressure of 2 MPa for 10 minutes and then heated in a drier at 180 DEG C for 1 hour to thermally cure the film adhesive to obtain a disc test piece having a diameter of 50 mm and a thickness of 5 mm. The thermal conductivity (W / m 占 K) of the test piece was measured by a heat flow method (according to JIS-A1412) using a thermal conductivity measuring device (trade name: HC-110, manufactured by Eco Seiki Seisakusho Co., Ltd.) .

(Extracted water electrical conductivity, ammonium ion concentration)

Approximately 10 g of the film-shaped adhesive before heat curing was cut out and heat treatment was performed at 180 캜 for 1 hour using a hot air oven to prepare a sample after heat curing. Approximately 2 g of the sample after thermosetting and 50 mL of pure water were placed in the vessel and subjected to a heat treatment at a temperature of 121 DEG C for 20 hours and the electrical conductivity of the obtained extracted water was measured by an electric conductivity meter (CYBERSCAN PC300 manufactured by EUTECH INSTRUMENTS). The ammonium ion concentration of the extracted water thus obtained was measured by ion chromatography [HIC-SP, manufactured by Shimadzu Seisakusho].

(Corrosion evaluation)

First, the obtained film-like adhesive was applied to a dummy silicon wafer (8 inch size, thickness 100 μm) at a temperature of 70 ° C. and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, Technovision Agency) Using a manual laminator, a dicing tape (trade name: K-13, manufactured by Furukawa Denki Kogyo Co., Ltd.) and a dicing frame (trade name: DTF2-8 -1H001, manufactured by DISCO Co., Ltd.] were put together to prepare a test piece. A dicing machine (trade name: DFD-6340 (trade name)) equipped with a biaxial dicing blade [Z1: NBC-ZH2030-SE (DD), manufactured by DISCO Co., Ltd. / Z2: NBC-ZH127F- , Manufactured by DISCO Co., Ltd.) to 7.5 x 7.5 mm in size, and a film-shaped adhesive section was manufactured.

Then, the film-shaped adhesive-added semiconductor chip was bonded to the lead frame substrate 1 under conditions of a temperature of 120 占 폚, a pressure of 0.1 MPa (load: 1000 gf) and a time of 1.0 second with a die bonder (trade name: DB-800 manufactured by Hitachi High- The film-shaped adhesive was thermally cured by being mounted on a [Material: 42Arroy-based metal, thickness: 125 m, manufactured by Toppan Printing Co., Ltd.] and heated at 150 占 폚 for 1 hour. Thereafter, the semiconductor chip and the lead frame substrate were bonded to each other with a copper wire (trade name: EX-1 (trade name), manufactured by Shin-Kawa KK) using a wire bonder (trade name: UTC- , 18 μm Φ, manufactured by NIPPON STEEL & SUMIKIN MATERIALS Co., Ltd.). Further, the film-shaped adhesive agent portion was mounted so as to be superimposed on the semiconductor chip on which the semiconductor chip was mounted first, and heated at 150 DEG C for 1 hour to thermally cure the film-shaped adhesive agent.

Thereafter, these semiconductor chips were sealed with a mold (trade name: KE-3000F5-2, Kyocera Corp.) as a mold apparatus (trade name: Y1E, manufactured by TOWA) Followed by heat treatment at 180 占 폚 for 5 hours to cure the mold agent to obtain a semiconductor package sample.

The resultant semiconductor package sample was subjected to a bias HAST test (temperature: 130 ° C, relative humidity: 85%, time: 100 hours), and then the cross section of the semiconductor package sample was observed under a table scanning electron microscope (Manufactured by JASCO International Co., Ltd.), the corrosion state of the copper circuit and the copper wire portion on the surface of the semiconductor chip was observed.

As a result of the observation, when the corrosion was not observed, it was judged that "A (good corrosion resistance)" and when the corrosion was observed, it was judged that "C (poor corrosion)".

(Blade abrasion evaluation)

First, the obtained film-like adhesive was applied to a dummy silicon wafer (8 inch size, thickness 100 μm) at a temperature of 70 ° C. and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, Technovision Agency) A dicing tape (trade name: G-11, manufactured by Lintec Corporation) and a dicing frame (trade name) were placed on the side opposite to the dummy silicon wafer of the film-shaped adhesive at room temperature and a pressure of 0.3 MPa using a manual laminator, (Trade name: DTF2-8-1H001, manufactured by DISCO Co., Ltd.). A dicing machine (trade name: DFD-6340 (trade name)) equipped with a biaxial dicing blade [Z1: NBC-ZH2030-SE (DD), manufactured by DISCO Co., Ltd. / Z2: NBC-ZH127F- , Manufactured by DISCO Co., Ltd.). The set-up was carried out before the dicing (before machining) and after the 150m cut (after machining), and the amount of blade blade tip projection was measured by non-contact type (laser type), and the amount of blade wear after machining - the projected amount of blade edge after machining). The yield was evaluated according to the following evaluation criteria.

[Evaluation standard]

A: Less than 10μm of wear

C: Wear amount of 10 μm or more

29 mass of a novolac phenolic resin (trade name: PS-4271, mass average molecular weight: 400, softening point: 70 캜, solid, hydroxyl equivalent: 105 g / eq, manufactured by Gakugei Kogyo Co., , 49 parts by mass of a bisphenol A type epoxy resin (trade name: YD-128, mass average molecular weight: 400, softening point: 25 占 폚 or less, liquid epoxy equivalent: 190, Shin-Nika Epoxy Seiko Kagaku Co., Ltd.) , 30 parts by mass of a copolymerized phenoxy resin (trade name: YP-70, mass average molecular weight: 55,000, Tg: 70 ° C, Shin-Nika Epoxy Seal Co., Ltd.) of A / bisphenol F, 3 parts by mass of S-510, 3-glycidyloxypropyltrimethoxysilane and JNC Corporation) were weighed, and 79 parts by mass of cyclopentanone was used as a solvent. In a 500 ml separable flask, Followed by heating and stirring at a temperature of 110 DEG C for 2 hours to obtain a resin varnish.

Next, 190 parts by mass of this resin varnish was transferred to an 800 ml planetary mixer, and then the mixture was immersed in a phosphoric acid water-treated aluminum nitride (trade name: HF-01A, average particle size 1.1 탆, Mohs hardness 8, thermal conductivity 200 W / m 占 토, (Manufactured by Tokuyama Corporation) and 0.8 part by mass of phosphorus-containing curing catalyst [trade name: TPP-K, manufactured by Hokko Corporation] were added, and the mixture was stirred at room temperature for 1 hour After stirring and mixing, vacuum defoaming was conducted to obtain a mixed varnish. Next, the obtained mixed varnish was coated on a mold release treated polyethylene terephthalate film (PET film) having a thickness of 38 mu m, followed by heating and drying (holding at 130 DEG C for 10 minutes) to obtain a film adhesive having a thickness of 20 mu m. The melt viscosity and thermal conductivity of the obtained film-form adhesive, the electrical conductivity of the extracted water, and the abrasion resistance of the blade were evaluated. The obtained results are shown in Table 1 together with the composition of the film-form adhesive.

Instead of 3 parts by mass of an epoxy-based silane coupling agent [trade name: S-510, 3-glycidyloxypropyltrimethoxysilane, JNC KABUSHIKI KAISHA] (Trade name: HF-01A, average particle diameter: 1.1 m, Mohs hardness: 8, thermal conductivity: 200 W / m 占,), and 3 parts by mass of phosphoric acid water-treated aluminum hydroxide (trade name: FOSPANOL RS-710, Toho Kagaku Co., Ltd.) (Trade name: HF-01, average particle size 1.1 mu m, Mohs hardness 8, thermal conductivity 200 W / (m · K), manufactured by TOKUYAMA KOGYO CO., LTD.) Was used instead of 273 parts by mass of a water- 273 parts by mass were used in place of the polyimide precursor, to obtain a composition for a film-form adhesive and a film-form adhesive.

Instead of 273 parts by mass of water-insolubilized aluminum nitride filler [trade name: HF-01, average particle diameter 1.1 m, Mohs hardness 8, thermal conductivity 200 W / m 占 제, manufactured by Tokuyama Co., ; Except that 273 parts by mass of polypropylene resin (HF-01A, average particle diameter 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / (m · K), manufactured by TOKUYAMA K.K.) An adhesive was obtained.

Phosphoric acid-treated water-resistant aluminum nitride [trade name; 283 parts by mass of HF-01A, average particle diameter of 1.1 m, Mohs hardness of 8, thermal conductivity of 200 W / m 占 토, manufactured by Tokuyama Co., Ltd.) (IXE-6107, bismuth-zirconium series, manufactured by TOAGOSEI KABUSHIKI KAISHA)] was used in place of the polyimide precursor, to obtain a composition for a film-form adhesive and a film-form adhesive.

Phosphoric acid-treated water-resistant aluminum nitride [trade name; 283 parts by mass of HF-01A, average particle diameter of 1.1 m, Mohs hardness of 8, thermal conductivity of 200 W / m 占 토, manufactured by Tokuyama Co., Ltd.) IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.) was used in place of the polyimide precursor, to obtain a composition for a film-form adhesive and a film-form adhesive.

Phosphoric acid-treated water-resistant aluminum nitride [trade name; 490 parts by mass of HF-01A, an average particle diameter of 1.1 m, a Mohs hardness of 8, a thermal conductivity of 200 W / m 占 토, manufactured by Tokuyama Co., Ltd.) IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.) was used in place of the above-mentioned component (A).

Phosphoric acid-treated water-resistant aluminum nitride [trade name; 169 parts by mass of HF-01A, average particle diameter of 1.1 m, Mohs hardness of 8, thermal conductivity of 200 W / m 占 토, manufactured by Tokuyama Co., Ltd.) IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.) was used in place of the above-mentioned component (A).

Phosphoric acid-treated water-resistant aluminum nitride [trade name; HF-01A, average particle diameter 1.1 m, Mohs hardness 8, thermal conductivity 200 W / m 占,, manufactured by TOKUYAMA CO., LTD.] And 134 parts by mass of ion trap (IXE-100, manufactured by Toagosei Co., Ltd., zirconium type, manufactured by TOAGOSEI KABUSHIKI KAISHA) was used in place of the above-mentioned binder resin.

(Comparative Example 1)

(Trade name: HF-01A) instead of 273 parts by mass of phosphoric acid water-treated aluminum nitride (trade name: HF-01A, average particle diameter 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / m · K, manufactured by TOKUYAMA CORPORATION) 01, an average particle diameter of 1.1 μm, a Mohs hardness of 8, a thermal conductivity of 200 W / (m · K), and 273 parts by mass of Toukyama Kogyo Co., Ltd.) .

(Comparative Example 2)

Instead of spherical alumina filler [trade name: AX3-15 R (trade name): HF-01A, average particle size 1.1 m, Mohs hardness 8, thermal conductivity 200 W / m 占,, manufactured by TOKUYAMA CORPORATION) , An average particle diameter of 3.0 μm, a Mohs hardness of 9, a thermal conductivity of 36 W / (m · K), and 453 parts by mass of Shin-Nihon Seitematerials Co., Ltd.) Shaped adhesive.

(Comparative Example 3)

A boron nitride filler (trade name: UHP-01, available from Showa Denko KK) was used in place of 273 parts by mass of phosphoric acid water-treated aluminum nitride [trade name: HF-01A, average particle size 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / m · K, , A composition for a film-like adhesive and a film (a film-forming composition) were prepared in the same manner as in Example 1 except that 92 parts by mass of a polyvinyl alcohol resin having an average particle size of 8.0 mu m, a Mohs hardness of 2, a thermal conductivity of 60 W / m · K, manufactured by SHOWA DENKO KOGYO Co., Shaped adhesive.

(Comparative Example 4)

(Trade name: HF-01A, average particle diameter 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / m · K, manufactured by Tokuyama Co., Ltd.) IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] was used in place of the above-mentioned component (A).

(Comparative Example 5)

605 parts by mass of a phosphoric acid-treated water-resistant aluminum nitride (trade name: HF-01A, average particle size 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / m · K, manufactured by TOKUYAMA CORPORATION) IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] was used in place of the silane coupling agent, and a film-like adhesive was obtained.

The obtained results are summarized in Tables 1 and 2 below.

The number representing the blending amount of the material is the mass part.

From the above Tables 1 and 2, the following points are apparent.

The epoxy resin curing agent, the phenoxy resin, and the aluminum nitride filler, and the content of the aluminum nitride filler was 30 to 60 vol% relative to the total amount of the resin and the filler as shown in Examples 1 to 8 %, And satisfies all the properties of the film-form adhesive specified in the present invention, so that generation of voids is suppressed while maintaining high thermal conductivity, and corrosion resistance and blade friction resistance are excellent.

On the other hand, in Comparative Example 1, the value of the electric conductivity of the extracted water was higher than that of Examples 1 and 2, and the corrosion resistance was lowered. It is estimated that the difference in the combination of the surface treatment agent and aluminum nitride is larger than the amount of ammonium ions generated in the bias HAST test.

On the other hand, in Comparative Examples 2 and 3 in which spherical alumina or boron nitride was used without using aluminum nitride filler, all of the characteristics of the film-like adhesive specified in the present invention were satisfied, in Comparative Example 2 using spherical alumina, Blade friction has dropped. Further, in Comparative Example 3 using boron nitride, voids were generated. The reason for this is believed to be that the boron nitride is in the form of flakes and is therefore based on the fact that the melt viscosity after blending in the resin binder is likely to rise compared to the spherical shape.

In Comparative Example 4 in which the content of the aluminum nitride filler relative to the total amount of the epoxy resin, the epoxy resin curing agent, the phenoxy resin, and the aluminum nitride filler was less than 30% by volume, the lowest melt viscosity and thermal conductivity were low. As a result, when the semiconductor chip provided with the film-form adhesive is mounted on the wiring board, the film-shaped adhesive tends to be easily peeled off, and the generated heat is hardly relieved to the outside of the package.

Conversely, in Comparative Example 5 in which the content of the aluminum nitride filler exceeded 60% by volume, the lowest melt viscosity and the electrical conductivity of the extracted water were high, voids were generated, and the corrosion resistance was also decreased.

While the present invention has been described in conjunction with the embodiments and the examples, we do not intend to limit our invention to any detail of the description unless specifically stated otherwise, and contrary to the spirit and scope of the invention set forth in the appended claims I think it should be widely interpreted without work.

The present application is based on Japanese Patent Application No. 2016-51630, filed on March 15, 2016, which is hereby incorporated by reference herein as part of the description of this specification.

1: semiconductor wafer
2: Film-shaped adhesive layer
3: Dicing tape
4: Semiconductor chip
5: Film-shaped adhesive portion semiconductor chip
6: wiring board
7: Bonding wire
8: Sealing resin
9: Semiconductor package

Claims (7)

A film-like adhesive composition comprising an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C) and an aluminum nitride filler (D)
Wherein the content of the aluminum nitride filler (D) is 30 to 60% by volume based on the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) Lt;
When the film adhesive obtained by the composition for film adhesive is heated at a temperature raising rate of 5 deg. C / minute at 25 deg. C, it reaches the lowest melt viscosity in the range of 200 to 10,000 Pa · s at 80 deg. C or higher, And the electric conductivity of the extracted water extracted into pure water at 121 占 폚 for 20 hours after thermosetting is 50 占 / / cm or less. . The method according to claim 1,
Characterized in that the aluminum nitride filler (D) has a surface oxidation layer on the surface of the filler and a water-repellent surface treatment with phosphoric acid or a phosphoric acid compound. 3. The method according to claim 1 or 2,
Further, it is preferable that the film composition contains an ion trap agent selected from a triazine thiol compound, a zirconium compound, an antimony bismuth compound and a magnesium aluminum compound in an amount of 1.0 to 3.0% by mass based on the aluminum nitride filler (D) Composition for an adhesive. A film-form adhesive obtained by the composition for a film-form adhesive according to any one of claims 1 to 3. A process for producing a film-shaped adhesive, characterized in that the composition for a film-form adhesive according to any one of claims 1 to 3 is coated on a release-treated base film and dried. A first step of thermally pressing the film adhesive and the dicing tape according to claim 4 onto a back surface of a semiconductor wafer having at least one semiconductor circuit formed on its surface to form an adhesive layer,
A second step of dicing the semiconductor wafer and the adhesive layer at the same time to obtain a semiconductor chip with the adhesive layer including the semiconductor wafer and the adhesive layer,
A third step of releasing the dicing tape from the adhesive layer and thermally bonding the adhesive layer to the semiconductor chip and the wiring substrate via the adhesive layer,
And a fourth step of thermally curing the adhesive layer. A semiconductor package obtained by the manufacturing method according to claim 6.

Images