KR102042516B1 - The composition for film adhesives, the film adhesive, the manufacturing method of a film adhesive, the semiconductor package using a film adhesive, and its manufacturing method - 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 vol with respect to the total amount of the epoxy resin, epoxy resin curing agent, phenoxy resin, and aluminum nitride filler. %, When the film adhesive obtained by the composition for film adhesives is heated at a temperature increase rate of 5 ° C./min at 25 ° C., the minimum melt viscosity in the range of 200 to 10000 Pa · s is reached at 80 ° C. or higher. The composition for film adhesives, film adhesives whose heat conductivity is 1.0 W / m * K or more hardened | cured body after thermosetting, and the electrical conductivity of the extraction water extracted in pure water at 121 degreeC 20 hours after thermosetting is 50 micrometers / cm or less The manufacturing method of a film adhesive, a semiconductor package, and its manufacturing method.

Description

The composition for film adhesives, the film adhesive, the manufacturing method of a film adhesive, the semiconductor package using a film adhesive, and its manufacturing method

This invention relates to the composition for film adhesives with high thermal conductivity, the film adhesive, the manufacturing method of a film adhesive, the semiconductor package using a film adhesive, and its manufacturing method.

In recent years, while miniaturization and high functionalization of electronic devices are in progress, high functionalization is progressing also in the semiconductor package mounted in the inside, and the refinement | miniaturization of the semiconductor wafer wiring rule is progressing. Accordingly, since heat tends to be generated on the surface of the semiconductor element, there is a problem that, for example, the operation speed of the semiconductor element is lowered or an operation defect of the electronic device is caused by the generated heat.

In order to eliminate such adverse influence by heat, the structural member of the semiconductor package is required for the thermal conductivity which relief | generates the heat which generate | occur | produced outside the package. Moreover, in what is called die attach material which joins between a semiconductor element and a wiring board, or between semiconductor elements, sufficient insulation and adhesive reliability are calculated | required with high thermal conductivity.

In addition, as such a die attach material, many conventionally used in paste form. However, in order to prevent contamination of other members such as semiconductor elements and wire pads due to resin flow, resin bleeding, etc., since high density mounting of the inside of the package is required with high performance of the semiconductor package, a film form (die (Attach film) is commonly used.

In order to achieve the die attach film high thermal conductivity, it is necessary to high charge the high thermal conductive filler. However, in general, when the filler filling amount is increased, the melt viscosity is easily increased, and when the die attach film is pasted on the back surface of the semiconductor wafer, or in the so-called die attach process in which a semiconductor element provided with the die attach film is mounted, the pasting step is performed. Adhesiveness between a die attach film and a to-be-adhered body falls at the time of temporary or the said mounting, and air becomes easy to roll in in the interface of both. This is based on the fact that the back surface of the semiconductor wafer and particularly the surface of the wiring board on which the semiconductor element is mounted are not necessarily smooth. Here, the air which has been dried not only reduces the adhesive force after heat curing of the die attach film, but also causes package cracks. Therefore, in order to suppress melt viscosity rise, it is necessary to make the filling amount as low as possible, to achieve high thermal conductivity, and to select a filler having higher thermal conductivity.

Moreover, in the manufacturing process of a semiconductor package, also in what is called a dicing process which cut | disconnects the semiconductor wafer in which the die attach film and the semiconductor element were formed simultaneously, it is also necessary that the wear rate of the processing blade by a die attach film is small. When a high hardness, high thermal conductivity filler is selected, the wear 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 process (dicing process). It becomes insufficient. In order to prevent this problem from occurring, increasing the frequency of blade replacement leads to an increase in cost because of a decrease in productivity. On the other hand, when a blade with a small amount of wear is used, chipping or the like that occurs in the wafer may occur. As a result, yield decreases.

In recent years, copper materials have been used for semiconductor members. For example, in order to reduce the cost of assembling a semiconductor package, the metal wire is made of a copper wire rather than a gold material which has been conventionally used. In addition, in order to improve the processing capability of the semiconductor device, a copper material having a lower electrical resistance is used for the semiconductor device circuit material than the aluminum material that has been conventionally used. However, when attaching a die attach film on such a copper semiconductor member, it is necessary that it does not corrode at the time of a reliability test, such as a bias HAST (Highly Accelerated Stress Test) under the high temperature, high humidity of a semiconductor package. For this reason, it is necessary for a die attach film to have few ionic impurities.

As described above, the high thermal conductivity die attach film includes i) low melt viscosity to express adhesion, ii) blade abrasion resistance in the dicing process, and iii) low ion impurity to prevent corrosion of the copper semiconductor member. Is required.

As a material which can be used for a high thermal conductivity die attach film, For example, in patent document 1, an epoxy resin, the polymer component of 95 degreeC or more of glass transition temperature, the polymer component of glass transition temperature of -30 degreeC or less, and thermal conductivity 10W / m. A high thermal conductive adhesive sheet composed of an inorganic filler of K or higher has been proposed. However, in the high thermal conductivity adhesive sheet described in patent document 1, although it has thermal conductivity and low melt viscosity, it can be estimated that the aluminum oxide of high hardness is used and the problem of blade abrasion resistance remains, and also There is also insufficient examination of ionic impurities.

Moreover, in patent document 2, the high thermally conductive resin composition containing the epoxy resin which has high thermally conductive particle | grains, mesogen, and a high molecular weight component is proposed. However, in the high heat conductive resin composition of patent document 2, although it has high thermal conductivity and adhesiveness, it can be estimated that the aluminum oxide of high hardness is used, and the problem of blade abrasion resistance remains, and also it is The review was also insufficient.

Moreover, in patent document 3, the sheet | seat of the heat conductive member which consists of a heat conductive filler which consists of aluminum hydroxide and silicon dioxide, and silicone type resin is proposed. However, in the sheet | seat of the heat conductive member described in patent document 3, although it has a high thermal conductivity to some extent, there exists still a problem about adhesiveness with a to-be-adhered body, and the examination about ionic impurities was also inadequate.

Japanese patent publication no. Japanese Unexamined Patent Publication No. 2013-6893 Japanese Unexamined Patent Publication No. 2009-286809

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and has excellent adhesion to the adherend, a small wear rate of the working blade, and low ion impurity for not corroding the copper semiconductor member. To provide a composition for film adhesives, a film adhesive, a method for producing a film adhesive, a semiconductor package using a film adhesive, and a method for producing the film adhesive capable of obtaining a film adhesive exhibiting excellent thermal conductivity after thermal curing. Shall be.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that it was achieved by the following structure as a result of earnestly researching in order to achieve the said subject.

(1) As a composition for film adhesives containing an epoxy resin (A), an epoxy resin hardener (B), a phenoxy resin (C), and an aluminum nitride filler (D), respectively,

Content of the said aluminum nitride filler (D) is 30-60 volume% with respect to the total amount of the said epoxy resin (A), the said epoxy resin hardener (B), the said phenoxy resin (C), and the said aluminum nitride filler (D). Is,

When the film adhesive obtained by the said composition for film adhesives was heated up at the temperature increase rate of 5 degree-C / min at 25 degreeC, it reached the minimum melt viscosity of the range of 200-10000 Pa.s at 80 degreeC or more, and thermosetting The composition for film adhesives after which a heat conductivity gives a hardened | cured body of 1.0 W / m * K or more, and the electrical conductivity of the extraction water extracted in pure water at 121 degreeC 20 hours after hardening is 50 microS / cm or less.

(2) The aluminum nitride filler (D) is a surface oxide layer on the surface of the filler The composition for film adhesives as described in (1) which is implemented and the water-resistant surface treatment with a phosphoric acid or a phosphoric acid compound is performed.

(3) An ion trapping 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). The composition for film adhesives as described in (1) or (2).

(4) The film adhesive obtained by the composition for film adhesives in any one of said (1)-(3).

(5) Coating and drying the composition for film adhesives as described in any one of said (1)-(3) on a release-processed base film, The manufacturing method of the film adhesive characterized by the above-mentioned.

(6) 1st process of thermocompression-bonding the film adhesive and dicing tape of (4) to the back surface of the semiconductor wafer in which the at least 1 semiconductor circuit was formed in the surface, and providing an adhesive bond layer,

A second step of obtaining an adhesive layer-added semiconductor chip comprising the semiconductor wafer and the adhesive layer by dicing the semiconductor wafer and the adhesive layer simultaneously;

A third step of detaching the dicing tape from the adhesive layer and thermally compressing the adhesive layer addition semiconductor chip and the wiring substrate through the adhesive layer;

And a fourth step of thermosetting the adhesive layer.

(7) The semiconductor package obtained by the manufacturing method as described in said (6).

Advantageous Effects of Invention According to the present invention, high heat excellence in adhesion to the adherend, the wear rate of the working blade is sufficiently small, and low ionic impurity is maintained so as not to corrode the copper semiconductor member, and excellent thermal conductivity after thermal curing It became possible to provide the composition for film adhesives which can obtain a conductive film adhesive, the film adhesive, the manufacturing method of a film adhesive, the semiconductor package using a film adhesive, and its manufacturing method.

The above, the other characteristics, and the advantage of this invention will become clear from the following description with reference to attached drawing suitably.

1 is a schematic longitudinal cross-sectional view showing one preferred embodiment of a first step of the method of manufacturing a semiconductor package of the present invention.
2 is a schematic longitudinal cross-sectional view showing one preferred embodiment of the second step of the method for manufacturing a semiconductor package of the present invention.
3 is a schematic longitudinal cross-sectional view showing one preferred embodiment of a third step of the method for manufacturing a semiconductor package of the present invention.
4 is a schematic longitudinal cross-sectional view showing one preferred embodiment of the step of connecting the bonding wires in the method of manufacturing a semiconductor package of the present invention.
5 is a schematic longitudinal cross-sectional view showing an example of a multi-stage stacking embodiment of the method for manufacturing a semiconductor package of the present invention.
6 is a schematic longitudinal cross-sectional view showing an example of another multi-stage stacking embodiment of the method for manufacturing a semiconductor package of the present invention.
7 is a schematic longitudinal cross-sectional view showing one preferred embodiment of a semiconductor package manufactured by the method for manufacturing a semiconductor package of the present invention.

<< composition for film adhesive >>

The composition for film adhesives of the present invention (hereinafter referred to as the composition for high thermal conductive film adhesives) includes an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and an aluminum nitride filler (D). It is 30-30 with respect to the total amount of the epoxy resin (A), epoxy resin hardening | curing agent (B), phenoxy resin (C), and aluminum nitride filler (D) which each contains and the content of the said aluminum nitride filler (D) contains. 60% by volume.

In addition, the high thermal conductive film adhesive obtained by the composition for high thermal conductive film adhesives of this invention has the temperature of 200-10000 Pa.s in 80 degreeC or more, when it heats up at the temperature increase rate of 5 degree-C / min at 25 degreeC. The minimum melt viscosity was reached, the thermal conductivity was 1.0 W / m · K or more after curing, and the electrical conductivity of the extracted water extracted in pure water at 121 ° C. for 20 hours after thermosetting was 50 μS / cm or less.

Here, after thermosetting in the measurement of thermal conductivity, the electrical conductivity of extracting water, and the ammonium ion concentration, it means after heating at least at 180 degreeC for 1 hour.

<Characteristics of Film Adhesive>

The minimum melt viscosity of the high thermal conductive film adhesive obtained with the composition for high thermal conductive film adhesives of this invention is 200-10000 Pa.s in 80 degreeC or more, when it heats up at the temperature increase rate of 5 degree-C / min at 25 degreeC. Reaches the lowest melt viscosity. The minimum melt viscosity is preferably in the range of 200 to 3000 Pa · s, particularly preferably in the range of 200 to 2000 Pa · s. When melt viscosity is larger than this range, a space | gap will remain easily between wiring board unevenness | corrugation when thermocompression bonding the semiconductor chip provided with the film adhesive on a wiring board. Moreover, when it is smaller than this range, when the semiconductor chip provided with the film adhesive is mounted on a wiring board, the flaw defect of a film adhesive will arise easily. In the present invention, the melt viscosity is measured by using a rheometer (trade name: RS6000, manufactured by Haake) and measuring the change in viscosity resistance in a temperature range of 25 to 200 ° C. and a temperature increase rate of 5 ° C./min. -It refers to the viscosity resistance when temperature is 80 degreeC or more in a viscosity resistance curve.

In order to make a minimum melt viscosity into the said range, in addition to content of an aluminum nitride filler (D), and also a kind of aluminum nitride filler (D), the coexistence of compounds, such as an epoxy resin (A) and an epoxy resin hardening | curing agent, or resin It can adjust with a kind and these content.

The heat conductivity of the high thermal conductive film adhesive of this invention is 1.0 W / m * K or more after thermosetting. As for thermal conductivity, 1.5 W / m * K or more is preferable. If the thermal conductivity is less than the lower limit, it tends to be difficult to relieve generated heat outside the package. In order to exert such excellent thermal conductivity after thermal curing, the high thermal conductive film adhesive of the present invention adheres the high thermal conductive film adhesive of the present invention to an adherend such as a semiconductor wafer or a wiring board and thermally cures the semiconductor package. The heat radiation efficiency to the outside is improved.

Although the upper limit of thermal conductivity is not specifically limited, In reality, it is 5.0 W / m * K or less.

In addition, in this invention, the heat conductivity of the film adhesive after such thermosetting is a heat flow meter method (JIS-) using a heat conductivity measuring apparatus (brand name: HC-110, the product of Eko Instruments Co., Ltd.). Thermal conductivity is measured according to A1412).

In order to make thermal conductivity into said range, in addition to content of an aluminum nitride filler (D), and also a kind of aluminum nitride filler (D), the kind of compound which coexists, such as an epoxy resin (A) and an epoxy resin hardening | curing agent, or resin, It can adjust with these content.

In addition, the high thermal conductive film adhesive of this invention is 50 microS / cm or less of the electrical conductivity of the extraction water extracted in pure water at 121 degreeC 20 hours after thermosetting. As for electrical conductivity, 40 micrometers / cm or less are preferable. When electrical conductivity exceeds the said upper limit, it becomes easy to corrode a copper material at the time of reliability test, such as bias HAST, under high temperature, high humidity of a semiconductor package.

The lower limit of the electrical conductivity is not particularly limited, but is in reality not less than 0.1 µS / cm.

In addition, in this invention, the electrical conductivity puts the film adhesive after thermosetting in pure water, and the electrical conductivity of the extraction water extracted by 121 degreeC 20 hours was made into the electrical conductivity meter (brand name: AE-200, METTLER TOLEDO). The value measured using the Gaisha (Mettler-Toledo International Inc.).

In order to make electric conductivity into the said range, it can adjust by using a phosphate ester type surfactant or an ion trapping agent (ion trapping agent) as surface modified aluminum nitride filler (D) and an additive.

<Epoxy Resin (A)>

The epoxy resin (A) contained in the composition for high thermal conductive film adhesives of this invention may be any of a liquid, solid, or semisolid. In the present invention, the liquid refers to a softening point of less than 50 ° C., the solid refers to a softening point of 60 ° C. or more, and the semi-solid indicates that the softening point is between the softening point of the liquid and the softening point of the solid (50 ° C. or more and 60 ° C.). Less than ℃). As the epoxy resin (A) used in the present invention, the softening point is 100 ° C or lower from the viewpoint of obtaining a film adhesive that can reach a low melt viscosity at a suitable temperature range (for example, 60 to 120 ° C). desirable. In addition, in this invention, a softening point is the value measured by the softening point test (circulation method) method (measurement condition: based on JIS-2817).

In the epoxy resin (A) used in the present invention, the crosslinking density of the cured product is increased, and as a result, a higher thermal conductivity is obtained because the contact probability between the aluminum nitride fillers (D) to be blended is high and the contact area is wider. From a viewpoint, it is preferable that it is 500 g / eq or less, and, as for an epoxy equivalent, it is more preferable that it is 150-450 g / eq. In addition, in this invention, epoxy equivalent means the number of grams (g / eq) of resin containing 1 gram equivalent of epoxy group.

As a skeleton of an epoxy resin (A), a phenol novolak type, an ortho cresol novolak type, a cresol novolak type, a dicyclopentadiene type, a biphenyl type, a fluorene bisphenol type, a triazine type, a naphthol type, a naphthalenediol type, Triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, trimethylol methane type, etc. are mentioned. Among them, the triphenylmethane type, bisphenol A type, cresol novolak type, orthocresol novolak type are preferable from the viewpoint of obtaining a film adhesive having low crystallinity and having a good appearance.

As for content of an epoxy resin (A), 3-30 mass% is preferable, and, as for content of the high thermal conductive film adhesive of this invention, 5-25 mass% is more preferable. When content is less than the said minimum, since the resin component which crosslinking density becomes high when it hardens | cures becomes small, there exists a tendency for the thermal conductivity of a film adhesive to become difficult to improve. There exists a tendency for a film state (film haze etc.) to change easily also in temperature change.

<Epoxy Resin Curing Agent (B)>

As an epoxy resin hardening | curing agent (B) contained in the composition for high thermal conductive film adhesives of this invention, well-known hardening | curing agents, such as amines, acid anhydrides, and polyhydric phenols, can be used. In this invention, the said epoxy resin (A) and the said phenoxy resin (C) become low melt viscosity, exhibit hardenability at the high temperature exceeding a certain temperature, have high speed hardenability, and long-term storage at room temperature It is preferable to use a latent hardening | curing agent from a viewpoint that the composition for film adhesives with high storage stability possible is obtained.

Examples of the latent curing agent include dicyandiamides, imidazoles, curing catalyst complex polyhydric phenols, hydrazides, boron trifluoride-amine complexes, amineimides, polyamine salts, and modified and microcapsule types thereof. Can be mentioned. In the present invention, the water absorption after thermal curing is lowered and the elasticity modulus after thermal curing is also lowered, and it is preferable to use a curing catalyst composite polyhydric phenols from the viewpoint that it is difficult to cause poor peeling in a moisture absorption reflow test after assembling a semiconductor package. More preferred.

As a curing catalyst composite type polyhydric phenol, a novolak-type phenol resin, a phenol aralkyl type phenol resin, a polyvinyl type phenol resin, a resor type phenol resin is mentioned, for example.

These may be used individually by 1 type, or may be used in combination of 2 or more type.

0.5-100 mass% is preferable with respect to the said epoxy resin (A), and, as for content of an epoxy resin hardening | curing agent (B), 1-80 mass% is more preferable. If the content is less than the lower limit, the curing time tends to be long. On the other hand, if the content exceeds the upper limit, excess curing agent remains in the film adhesive, and the remaining curing agent adsorbs moisture. There exists a tendency for a defect to become easy to produce in a test.

<Phenoxy Resin (C)>

As a phenoxy resin (C) contained in the composition for high thermal conductive film adhesives of this invention, it is used in order to provide sufficient adhesiveness and film forming property (film formability) to a film forming layer. The phenoxy resin has a similar structure to that of the epoxy resin, and therefore has good compatibility, low resin melt viscosity, and good adhesion. The phenoxy resin is obtained from bisphenol and epichlorohydrin such as bisphenol A, and in the present invention, the mass average molecular weight is preferably 10,000 or more thermoplastic resin. By mix | blending a phenoxy resin, it is effective in eliminating turbidity, fragility, etc. at normal temperature. Preferable phenoxy resins include bisphenol A type, bisphenol A / F type, bisphenol F type, and cardo-skeleton type phenoxy resins. The phenoxy resin is 1256 (brand name: bisphenol A type phenoxy resin, product of Mitsubishi Chemical Co., Ltd.), YP-70 (brand name: bisphenol A / F type phenoxy resin, Shin-Nikka epoxy Seijo Chemical Co., Ltd., FX-316 (brand name: bisphenol F-type phenoxy resin, Shin-Nikka Epoxy Co., Ltd.), and FX-280S (brand name: Carr) Commercially available phenoxy resins such as skeletal phenoxy resins and manufactured by Shin-Nika Chemical Co., Ltd. may be used.

Here, a mass average molecular weight is the value calculated | required by polystyrene conversion by GPC (Gel Permeation Chromatography).

The glass transition temperature (Tg) of the phenoxy resin is preferably less than 100 ° C, and particularly preferably less than 80 ° C.

Moreover, 0 degreeC or more is preferable and, as for the minimum of glass transition temperature (Tg), 10 degreeC or more is more preferable.

1-20 mass% is preferable with respect to an epoxy resin (A), 3-15 mass% is more preferable, and, as for content of a phenoxy resin, 4-13 mass% is more preferable. By making content into these ranges, a film state will be favorable (film haze) and it can also suppress film fragility.

<Aluminum Nitride Filler (D)>

As an aluminum nitride filler (D) contained in the composition for high thermal conductive film adhesives of this invention, it contributes to high thermal conductivity of a film adhesive, and reduction of a linear expansion coefficient. If the value of the coefficient of linear expansion is high, the difference in the coefficient of linear expansion with the wiring board becomes large. Therefore, the effect of suppressing the stress with these to-be-adhered objects is low, and it is undesirable because it is connected to generating a package crack.

Generally, since aluminum nitride has low affinity with resin, the thermal resistance at the interface with resin tends to increase. In addition, since the reactivity with water is high, the surface is hydrolyzed by contact with water in a powder state, and it is easy to produce ammonia. This ammonia becomes ammonium ion, and it becomes easy to corrode a copper material at the time of reliability test, such as bias HAST, at high temperature, high humidity of a semiconductor package. For this reason, in this invention, it is preferable that aluminum nitride filler (D) is surface-modified. As a surface modification method of aluminum nitride, the method of providing the oxide layer of aluminum oxide in a surface layer to improve water resistance, and surface-treatment with phosphoric acid or a phosphoric acid compound, and improving affinity with resin are preferable.

Phosphoric acid used in the surface treatment is ortho phosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ O ₇ ), metaphosphoric acid ((HPO ₃ ) n, n is an integer indicating the degree of condensation) or their metal salt Can be mentioned. Examples of the phosphoric acid compound include organic phosphoric acids such as alkylphosphonic acid, arylphosphonic acid, alkyl phosphoric acid and aryl phosphoric acid (for example, methylphosphonic acid, ethylphosphonic acid, hexylphosphonic acid, vinylphosphonic acid, phenylphosphonic acid, methyl phosphoric acid and ethyl). Phosphoric acid, hexyl phosphoric acid).

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

Moreover, it is also preferable to use an ion trap agent (ion trapping agent) together.

In this invention, content of an aluminum nitride filler (D) is 30-30 with respect to the total amount of the said epoxy resin (A), the said epoxy resin hardening | curing agent (B), the said phenoxy resin (C), and the said aluminum nitride filler (D). It is 60 volume%, and it is more preferable to mix | blend 35-50 volume%. This is because the minimum melt viscosity value is controlled by the aluminum nitride filler compounding amount. When the compounding quantity is larger than the range, the minimum melt viscosity value is increased, and when the semiconductor chip provided with the present film adhesive is thermocompressed on the wiring board, voids are likely to remain between the wiring board irregularities, and the film fragility becomes stronger. When the compounding quantity is less than the range, the minimum melt viscosity value is small, and the defect of the film adhesive is easily generated when the semiconductor chip provided with the film adhesive is mounted on the wiring board.

In the present invention, the aluminum nitride filler (D) is preferably spherical from the viewpoint of high filling and fluidity. Moreover, it is preferable that an average particle diameter is 0.01-5 micrometers. When the particle size is smaller than 0.01 μm, the filler tends to aggregate, unevenness may occur during film production, and the uniformity of the film thickness of the obtained adhesive film may deteriorate. When the particle size is larger than 5 µm, when the thin film is produced by a coating machine such as a roll knife coater, the filler is synchronized to easily generate streaks on the film surface.

The aluminum nitride (D) used in the present invention preferably has a Mohs hardness of 7 to 8. When Mohs' Hardness exceeds the said upper limit, the wear rate of the processing blade by a film adhesive becomes large. In the present invention, the Mohs hardness is measured using a ten-stage Mohs hardness tester, sequentially scratched from a small mineral of hardness to the measurement object, and visually measuring whether the measurement object is damaged or not, and determining the hardness of the measurement object. Say a value.

In addition, in this invention, an average particle diameter means the particle diameter at which 50% accumulates when the total volume of particle | grains is 100% in a particle size distribution, and a laser diffraction and scattering method (measurement condition: dispersion medium-hexamethic phosphate Sodium, laser wavelength: 780 nm, measuring device: microtrack MT3300EX) can be calculated | required from the cumulative curve of the volume fraction of the particle diameter of the particle size distribution measured by. In addition, in this invention, a spherical shape means a spherical or substantially spherical spherical shape with no angle.

As a method of mix | blending an aluminum nitride filler (D) with a resin binder, the method of directly mix | blending a silane coupling agent, a phosphoric acid or a phosphate compound, and surfactant as needed (integral blend method), or as needed The method of mix | blending the slurry state aluminum nitride filler which disperse | distributed the aluminum nitride filler processed by the surface treating agent, such as a silane coupling agent, a phosphoric acid compound or a phosphoric acid compound, and surfactant, can be used. In particular, when producing a thin film, it is more preferable to use a slurry state aluminum nitride filler. This is to mix resin components, such as an epoxy resin, an epoxy resin hardening | curing agent, and a polymer, with the surface treatment aluminum nitride filler dispersion liquid disperse | distributed in the smaller organic solvent, and even the aluminum nitride filler with a small particle diameter is uniform without being aggregated in a resin component. It is because it can disperse | distribute and the surface external appearance of the film adhesive obtained will become favorable.

The silane coupling agent combines at least one hydrolyzable group, such as an alkoxy group and an aryloxy group, with the silicon atom, and may add an alkyl group, an alkenyl group, and an aryl group in addition to this. 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), or (meth) acryl. It is more preferable that the monooxy group is substituted.

The silane coupling agent is, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-metha Cryloyl oxypropyl methyl diethoxy silane, 3-methacryloyl oxypropyl triethoxy silane, etc. are mentioned.

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

In this invention, anionic surfactant is preferable and a phosphate ester type surfactant is more preferable.

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

In General formula (1), R <^1> represents an alkyl group, an alkenyl group, or an aryl group, L <^1> represents an alkylene group, m represents the integer of 0-20, n represents 1 or 2.

1-20 are preferable, as for carbon number of the alkyl group in R <^1> , 8-20 are more preferable, 8-18 are more preferable, For example, butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl Hexyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl are mentioned, decyl, undecyl, and dodecyl are preferable, and undecyl is especially preferable.

2-20 are preferable, as for carbon number of the alkenyl group in R <^1> , 8-20 are more preferable, 8-18 are more preferable, For example, allyl and oleyl are mentioned.

6-20 are preferable, as for carbon number of the aryl group in R <^1> , 6-20 are more preferable, 6-18 are more preferable, For example, phenyl and nonylphenyl are mentioned.

2 or 3 is preferable, as for carbon number of the alkyl group in L <^1> , 2 is more preferable, for example, ethylene and propylene are mentioned.

m is preferably an integer of 0 to 10.

The phosphate ester represented by General formula (1) may be a mixture of n and 1.

The phosphate ester represented by General formula (1) can use what is marketed as a phosphanol series by Toho Chemical Co., Ltd .. For example, phosphanol RS-410, 610, 710, phosphanol RL-310, phosphanol RA-600, phosphanol ML-200, 220, 240, phosphanol GF-199 (all are brand names) is mentioned.

It is preferable to contain 0.1-5.0 mass% of silane coupling agents and surfactant with respect to an aluminum nitride filler (D).

When content of a silane coupling agent and surfactant is less than the said minimum, an aluminum nitride filler (D) will aggregate easily and the external appearance of a film surface will deteriorate. On the other hand, if it is more than the said upper limit, the excess silane coupling agent and surfactant which remain in the system will volatilize in a semiconductor assembly heating process (for example, a reflow process), and will cause peeling at an adhesive interface.

<Other additives>

As a composition for film adhesives of this invention, in addition to the said epoxy resin (A), the said epoxy resin hardener (B), the said phenoxy resin (C), and the said aluminum nitride filler (D), the effect of this invention is not impaired. In the range which does not carry out, you may further contain additives, such as an ion trapping agent (ion trapping agent), a hardening catalyst, a viscosity modifier, antioxidant, a flame retardant, a coloring agent, stress relief agents, such as butadiene type rubber and silicone rubber.

Among these, it is preferable to use an ion trapping agent especially for the purpose of supplementing the ammonium ion which arises by hydrolysis of aluminum nitride with water. As an ion trap agent, the inorganic ion trap agent containing a triazine thiol compound, a zirconium type compound, an antimony bismuth type compound, and a magnesium aluminum type compound is mentioned.

As for an ion trap agent, it is more preferable to use 1.0-3.0 mass% with respect to an aluminum nitride filler (D).

If the content of the ion trapping agent is less than the above lower limit, the generated ammonium ions remain in the system, and it is easy to cause corrosion of the circuit member during the reliability test. On the other hand, when the said upper limit is exceeded, the excess ion trap agent remaining in a system will absorb moisture, and the adhesive force of an adhesive interface will fall easily, and it will cause peeling at the time of a reliability test.

In this invention, in the measurement conditions of the said wastewater electrical conductivity, 80 ppm or less is preferable and, as for ammonium ion concentration, 70 ppm or less is more preferable.

When the ammonium ion concentration exceeds the above upper limit, the concentration of ammonium ions or other ionic impurities becomes high, and corrosion of the circuit member easily occurs during the reliability test.

Moreover, in this invention, it is also preferable to use a curing catalyst. Examples of the curing catalyst include a phosphorus-boron type curing catalyst, a triphenylphosphine type curing catalyst, an imidazole type curing catalyst, and an amine type curing catalyst, and a phosphorus-boron type curing catalyst and a triphenylphosphine type curing catalyst are preferable. Phosphorus-boron type curing catalysts are preferred among them.

Examples of the triphenylphosphine type curing catalyst include triaryl phosphines such as triphenylphosphine and tri-p-tolylphosphine, and are preferable.

Examples of the phosphorus-boron type curing catalyst include tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; TPP-MK), and triphenylphosphine triphenylborane (trade name). Phosphorus-boron-type hardening accelerators, such as TPP-S) (all are the Hokokagaku Kogyo Co., Ltd. make). In the present invention, among these, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetra-p-triborate are preferable from the viewpoint of excellent latent stability at room temperature.

It is preferable to make a curing catalyst contain 0.1-5.0 mass% with respect to an epoxy resin hardening | curing agent (B).

<< film adhesive and its manufacturing method >>

As one suitable embodiment of the manufacturing method of the film adhesive of this invention, the method of coating the composition for high thermal conductive film adhesives of this invention on one surface of the base film processed by the release process, and carrying out heat drying is mentioned. However, this method is not particularly limited. As a base film which carried out the mold release process, it should just function as a cover film of the film adhesive obtained, and a well-known thing can be employ | adopted suitably. For example, a release processed polypropylene (PP), a release processed polyethylene (PE), and a release processed polyethylene terephthalate (PET) can be mentioned. As a coating method, a well-known method can be employ | adopted suitably, For example, the method using a roll knife coater, a gravure coater, a die coater, a reverse coater, etc. is mentioned.

As the film adhesive of this invention obtained in this way, 5-200 micrometers in thickness is preferable, and 5-40 micrometers is more preferable from a viewpoint that the unevenness | corrugation of a wiring board and the surface of a semiconductor chip can be fully filled. If the thickness is less than the lower limit, there is a tendency that the unevenness of the wiring board and the surface of the semiconductor chip is not sufficiently embedded, and sufficient adhesion cannot be ensured. On the other hand, if the upper limit is exceeded, it is difficult to remove the organic solvent at the time of manufacture. Since the amount of residual solvent increases, film turbidity tends to be strong.

<< semiconductor package and manufacturing method thereof >>

EMBODIMENT OF THE INVENTION Next, preferred embodiment of the semiconductor package of this invention and its manufacturing method is demonstrated in detail, referring drawings. In addition, in the following description and drawings, the same code | symbol is attached | subjected to the same or corresponding element, and the overlapping description is abbreviate | omitted. 1-7 is a schematic longitudinal cross-sectional view which shows one suitable embodiment of each process of the manufacturing method of the semiconductor package of this invention.

In the manufacturing method of the semiconductor package of this invention, first, as a 1st process, as shown in FIG. 1, the film shape of the said invention on the back surface of the semiconductor wafer 1 in which the at least 1 semiconductor circuit was formed in the surface. The adhesive agent is thermocompression-bonded to provide the adhesive layer 2, and then the semiconductor wafer 1 and the dicing tape 3 are provided via the adhesive layer 2. At this time, the product in which the adhesive layer 2 and the dicing tape 3 are integrated may be thermocompressed at a time. As the semiconductor wafer 1, a semiconductor wafer having at least one semiconductor circuit formed on its surface can be appropriately used, and examples thereof include silicon wafers, SiC wafers, and GaS wafers. As the adhesive layer 2, the high thermal conductive film adhesive of this invention may be used individually by 1 layer, or you may laminate and use 2 or more layers. As a method of providing such an adhesive layer 2 on the back surface of the wafer 1, a method capable of laminating the film adhesive on the back surface of the semiconductor wafer 1 can be appropriately employed. After pasting the said film adhesive on the back surface, when laminating | stacking two or more layers, it is a method of laminating | stacking a film adhesive one by one until it becomes desired thickness, or after laminating | stacking a film adhesive to the target thickness previously, a semiconductor The method of sticking to the back surface of the wafer 1, etc. are mentioned. Moreover, it does not specifically limit as an apparatus used when providing this adhesive bond layer 2 in the back surface of the semiconductor wafer 1, For example, well-known apparatuses, such as a roll laminator and a manual laminator, can be used suitably.

Next, as a 2nd process, as shown in FIG. 2, the adhesive bond layer provided with the semiconductor wafer 1 and the adhesive bond layer 2 is added by dicing the semiconductor wafer 1 and the adhesive bond layer 2 simultaneously. The semiconductor chip 5 is obtained. It does not restrict | limit especially as the dicing tape 3, A well-known dicing tape can be used. Moreover, the apparatus used for dicing is not specifically limited, either, A well-known dicing apparatus can be used suitably.

Next, as a 3rd process, as shown in FIG. 3, the dicing tape 3 is peeled off from the adhesive bond layer 2, and the adhesive bond layer 2 is connected to the semiconductor chip 5 and the wiring board 6 with an adhesive bond layer 2, and the adhesive layer 2 is carried out. The thermocompression bonding is carried out through), and the adhesive bond layer addition semiconductor chip 4 is mounted on the wiring board 6. As the wiring board 6, the board | substrate with which the semiconductor circuit was formed in the surface can be used suitably, For example, printed circuit board (PCB), various lead frames, and electronic components, such as a resistance element and a capacitor, are mounted on the board surface. Substrates can be cited.

The method of mounting the adhesive layer-added semiconductor chip 5 on the wiring board 6 is not particularly limited, and the adhesive layer-added semiconductor chip 5 is used for the wiring board 6 or the wiring board. The conventional method which can adhere to the electronic component mounted on the surface of (6) can be employ | adopted suitably. As such a mounting method, conventionally known heating and pressing methods such as a method using a mounting technique using a flip chip bonder having a heating function from the top, a method using a die bonder having a heating function only from the bottom, and a method using a laminator Can be mentioned.

As described above, the adhesive layer-added semiconductor chip 5 is mounted on the wiring board 6 via the adhesive layer 2 made of the film adhesive of the present invention, and thus, on the wiring board 6 generated by the electronic component. Since the film adhesive can follow the unevenness, the semiconductor chip 4 and the wiring board 6 can be brought into close contact and fixed.

Next, as a 4th process, the film adhesive of this invention is thermosetted. There is no restriction | limiting in particular if it is more than the thermosetting start temperature of the film adhesive of this invention as a temperature of thermosetting, It is different by the kind of resin to use, It cannot say collectively, For example, 100-180 C is preferable and 140-180 degreeC is more preferable from a viewpoint that hardening at higher temperature can harden in a short time. When temperature is less than thermosetting start temperature, thermosetting does not fully advance but the intensity | strength of the adhesive layer 2 tends to fall, On the other hand, when it exceeds the said upper limit, the epoxy resin in a film adhesive, a hardening | curing agent, or an additive during a hardening process It tends to volatilize and foam easily. In addition, as for time of a hardening process, 10 to 120 minutes are preferable, for example. In the present invention, by thermally curing the film adhesive at a high temperature, a semiconductor package in which the wiring board 6 and the semiconductor chip 4 are firmly adhered to each other can be obtained without voids even when cured at a high temperature. .

Next, in the manufacturing method of the semiconductor package of this invention, as shown in FIG. 4, it is preferable to connect the wiring board 6 and the adhesive bond layer addition semiconductor chip 5 via the bonding wire 7. There is no restriction | limiting in particular as such a connection method, A conventionally well-known method, for example, the wire bonding method, the TAB (Tape Automated Bonding) method, etc. can be employ | adopted suitably.

In addition, a plurality of semiconductor chips 4 can be laminated on the surface of the mounted semiconductor chip 4 by thermocompression bonding and thermosetting other semiconductor chips 4 and connecting the wiring substrate 6 again by a wire bonding method. For example, as shown in FIG. 5, the method of laminating | stacking a semiconductor chip by shift | deviating, or the method of laminating | stacking while bonding the bonding wire 7 by filling the 2nd-layer adhesive layer 2 as shown in FIG. There is this.

In the manufacturing method of the semiconductor package of this invention, as shown in FIG. 7, it is preferable to seal the wiring board 6 and the adhesive bond layer addition semiconductor chip 5 with the sealing resin 8, In this way, it is a semiconductor package. (9) can be obtained. It does not restrict | limit especially as sealing resin 8, The appropriately well-known sealing resin which can be used for manufacture of a semiconductor package can be used. Moreover, it does not specifically limit also as the sealing method by the sealing resin 8, It is possible to employ | adopt a well-known method suitably.

According to the manufacturing method of the semiconductor package of this invention, the adhesive bond layer 2 which is excellent in adhesiveness with a to-be-adhered body, the wear rate of a process blade is sufficiently small, and does not corrode a copper semiconductor member can be provided. In addition, by exhibiting excellent thermal conductivity after thermosetting, heat generated on the surface of the semiconductor chip 4 can be efficiently released to the outside of the semiconductor package 9.

EXAMPLE

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, in each Example and the comparative example, melt viscosity, thermal conductivity, extract water electrical conductivity, blade wear rate, and corrosiveness evaluation were each implemented by the method shown below.

(Measurement of the minimum melt viscosity)

The film adhesive obtained in each Example and the comparative example was cut out and laminated | stacked in the size of 5.0 cm x 5.0 cm, and it bonded together with the hand roller on the hotplate of stage 70 degreeC, and obtained the test piece whose thickness is about 1.0 mm. About this test piece, the change of viscosity resistance in a temperature range of 20-250 degreeC and a temperature increase rate of 5 degree-C / min is measured using a rheometer [RS6000, Haake make], and the minimum melt viscosity is obtained from the obtained temperature-viscosity resistance curve. (Pa · s) was calculated.

(Void evaluation)

First, the film adhesive obtained in each Example and the comparative example is piled in the temperature of 70 degreeC, and the pressure of 0.3 MPa using a manual laminator [brand name: FM-114, the product made by TECHNO VISION, INC.] After adhering to one surface of the glass substrate (10x10cm, thickness 50 micrometers) as a silicon wafer, using the said manual laminator, it is a side opposite to the glass substrate as the said dummy silicon wafer of a film adhesive at room temperature and pressure 0.3MPa using the said 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 adhered on the surface of the substrate. Next, a dicing apparatus [brand name: DFD-6340, product made by DISCO] provided with a biaxial dicing blade [Z1: NBC-ZH2050 (27HEDD), product made by DISCO / Z2: NBC-ZH127F-SE (BC), product made by DISCO] The glass chip which is a dummy semiconductor chip was obtained by dicing so that it might become a size of 10 mm x 10 mm using the following.

Next, the glass chip was subjected to a die bonder (trade name: DB-800, manufactured by Hitachi High-Technologies Corporation.) At a temperature of 120 ° C., a pressure of 0.1 MPa (load 1000 gf), and a time of 1.0 second. Was thermocompression-bonded on the wiring board (FR-4 board | substrate, 200 micrometers in thickness). The state in the film adhesive after thermocompression bonding was observed from the glass substrate back surface. The void evaluation was evaluated according to the following evaluation criteria.

[Evaluation standard]

A: No void

C: voids occur

(Thermal conductivity)

The obtained film adhesive is cut out into square pieces 50 mm or more on one side, the cut samples cut together so that thickness may be 5 mm or more, are put on the disk-shaped metal mold | die of diameter 50mm and thickness 5mm, and the temperature is 150 using a compression press molding machine. The film adhesive was thermosetted by heating for 10 minutes at 0 degreeC and pressure 2 Mpa, and also heating at 180 degreeC in a dryer for 1 hour, and the disk shaped test piece of diameter 50mm and thickness 5mm was obtained. About this test piece, the thermal conductivity (W / m * K) was measured by the heat flow method (according to JIS-A1412) using the thermal conductivity measuring apparatus (brand name: HC-110, the product made by Eco Seiki Co., Ltd.). .

(Extract Water Electrical Conductivity, Ammonium Ion Concentration)

About 10 g of the film adhesive before thermosetting was cut out, the heat processing for 1 hour was performed at 180 degreeC using the hot air oven, and the sample after thermosetting was produced. About 2 g of the sample after thermosetting and 50 mL of pure water were put into the container, and heat processing was performed at the temperature of 121 degreeC for 20 hours, and the electrical conductivity of the obtained extract water was measured with the electric conductivity meter (CYBERSCAN PC300 made from EUTECH INSTRUMENTS). In addition, the ammonium ion concentration of the obtained extract water was measured by ion chromatography [HIC-SP, Shimadzu Corporation].

Corrosion Assessment

First, the obtained film adhesive is stuck to a dummy silicon wafer (8 inch size, thickness 100 micrometers) at the temperature of 70 degreeC, and a pressure of 0.3 MPa using a manual laminator (brand name: FM-114, the product made by Technovision Co., Ltd.). Dicing tape [brand name: K-13, Furukawa Denki Kogyo Co., Ltd.] and dicing frame [brand name: DTF2-8 on the surface side opposite to the dummy silicon wafer of a film adhesive at room temperature and pressure 0.3MPa using a manual laminator -1H001, manufactured by DISCO Corporation] was used as a test piece. The dicing apparatus [brand name: DFD-6340] provided with the biaxial dicing blade [Z1: NBC-ZH2030-SE (DD), DISCO company / Z2: NBC-ZH127F-SE (BB), DISCO company] with respect to this test piece. , Made by DISCO Corporation], dicing was performed at a size of 7.5 × 7.5 mm, and a film adhesive addition semiconductor chip was produced.

Next, the film adhesive-attached semiconductor chip was placed on a lead frame substrate using a die bonder (brand name: DB-800, manufactured by Hitachi Hi-Tech Co., Ltd.) at a temperature of 120 ° C., a pressure of 0.1 MPa (load of 1000 gf), and a time of 1.0 second. [Material: 42 Arroy-based metal, thickness: 125 μm, manufactured by Nippon Insatsu Corp.] The film adhesive was thermally cured by heating at 150 ° C. for 1 hour. Subsequently, the semiconductor chip and the lead frame substrate were copper wires at a stage temperature of 200 ° C. using a wire bonder (trade name: UTC-3000, manufactured by Shinkawa Co., Ltd.). , 18 um Φ, manufactured by NIPPON STEEL & SUMIKIN MATERIALS Co., Ltd.]. Moreover, the film adhesive was thermosetted by mounting so that the said film adhesive addition semiconductor chip may be superimposed on the semiconductor chip which mounted first, and heating at 150 degreeC for 1 hour.

Thereafter, these semiconductor chips were sealed by a mold apparatus [trade name: KE-3000F5-2, manufactured by Kyocera Corp.] with a mold apparatus (trade name: Y1E, manufactured by TOWA), and the temperature was increased. The heat treatment was performed at 180 degreeC for 5 hours, the mold agent was hardened | cured, and the semiconductor package sample was obtained.

After the bias HAST test (temperature: 130 ° C., relative humidity: 85%, time: 100 hours) was performed on the obtained semiconductor package sample, the cross section of the semiconductor package sample was subjected to a table-top scanning electron microscope [trade name: Pro, Jasco Made by JASCO International Co., Ltd.], the corrosion state of the copper circuit and the copper wire part of the semiconductor chip surface was observed.

As a result of observation, when corrosion was not observed, it was determined as "A (good corrosion resistance)", and when corrosion was observed, it was determined as "C (bad corrosion resistance)".

(Blade Wear Evaluation)

First, the obtained film adhesive is stuck to a dummy silicon wafer (8 inch size, thickness 100 micrometers) at the temperature of 70 degreeC, and a pressure of 0.3 MPa using a manual laminator (brand name: FM-114, the product made by Technovision Co., Ltd.). Using a manual laminator, a dicing tape (trade name: G-11, manufactured by Lintec Corporation) and a dicing frame on the surface side opposite to the dummy silicon wafer of the film adhesive at room temperature and pressure of 0.3 MPa. [Product name: DTF2-8-1H001, manufactured by DISCO Corporation] were put together to make a test piece. The dicing apparatus [brand name: DFD-6340] provided with the biaxial dicing blade [Z1: NBC-ZH2030-SE (DD), DISCO company / Z2: NBC-ZH127F-SE (BB), DISCO company] with respect to this test piece. Made by DISCO Co., Ltd.] at a size of 1.0 × 1.0 mm. Set up before dicing (before processing) and 150m cut time (after processing), and measuring blade blade protrusion by non-contact type (laser type), and the amount of blade wear after machining (blade blade protrusion before processing) -Blade blade protrusion amount after processing) was calculated. The yield was evaluated according to the following evaluation criteria.

[Evaluation standard]

A: Abrasion less than 10 μm

C: at least 10 μm

Novolak-type phenolic resin [brand name: PS-4271, mass average molecular weight: 400, softening point: 70 degreeC, solid, hydroxyl equivalent: 105 g / eq, Guneikagaku Chemical Co., Ltd.] 29 mass 49 parts by mass of bisphenol A type epoxy resin [trade name: YD-128, mass average molecular weight: 400, softening point: 25 ° C or lower, liquid, epoxy equivalent: 190, manufactured by Shin-Nikaka Epoxy Co., Ltd.], and bisphenol Copolymer-type phenoxy resin of A / bisphenol F [brand name: YP-70, mass average molecular weight: 55,000, Tg: 70 degreeC, the product made by Shin-Nikka Epoxy Co., Ltd.] 30 mass parts, epoxy type silane coupling agent [brand name: S-510, 3-glycidyloxypropyltrimethoxysilane and manufactured by JNC Corporation (JNC Corporation.), 3 parts by mass are weighed, and 79 parts by mass of cyclopentanone is used as a solvent in a 500 ml separable flask. It heated and stirred at the temperature of 110 degreeC for 2 hours, and obtained the resin varnish.

Next, 190 mass parts of this resin varnish was transferred to a 800 ml planetary mixer, and phosphoric acid water-treated aluminum nitride [brand name: HF-01A, average particle diameter 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / mK, Kabushi Kaishitoku, 273 parts by mass of Yamato (Tokuyama Corporation), 0.8 parts by mass of a phosphorus-boron type curing catalyst [trade name: TPP-K, manufactured by Hokoka Chemical Co., Ltd., tetraphenylphosphonium tetraphenylborate] was added, and 1 hour at room temperature. After stirring and mixing, vacuum defoaming was performed to obtain a mixed varnish. Next, the obtained mixed varnish was applied onto a release-treated polyethylene terephthalate film (PET film) having a thickness of 38 µm and heated and dried (holding at 130 ° C. for 10 minutes) to obtain a film adhesive having a thickness of 20 µm. Melt viscosity, thermal conductivity, extract water electrical conductivity, and corrosiveness of the obtained film adhesive were evaluated. The obtained result is shown in Table 1 with the composition of a film adhesive.

Epoxy silane coupling agent [brand name: S-510, 3-glycidyloxypropyl trimethoxysilane, JNC Corporation] Instead of 3 mass parts, phosphoric acid ester type surfactant [brand name; Phosphoric acid water treatment aluminum nitride [brand name: HF-01A, average particle diameter 1.1μm, Mohs' hardness 8, thermal conductivity 200W / m * K], using 3 mass parts of phosphanol RS-710 and Tohoka Chemical Co., Ltd. product. Shikiisha Shatokuyama Co., Ltd.) Water-resistant untreated aluminum nitride filler [brand name: HF-01, average particle diameter 1.1μm, Mohs' Hardness 8, heat conductivity 200W / (mK), made by Kabushiki Shatokuyama Co., Ltd.] instead of 273 parts by mass] Except having used 273 mass parts, it carried out similarly to Example 1, and obtained the composition for film adhesives and a film adhesive.

Water-resistant unprocessed aluminum nitride filler [brand name: HF-01, average particle diameter 1.1μm, Mohs hardness 8, thermal conductivity 200W / m * K, product made from Kabushiki Shatokuyama] Phosphoric acid water-resistant aluminum nitride instead of 273 mass parts ; HF-01A, average particle diameter 1.1 μm, Mohs hardness 8, thermal conductivity 200 W / (m · K), manufactured by Kabushiki Shatokuyama Co., Ltd., except that 273 parts by mass were used, and the composition for a film adhesive and a film shape were prepared in the same manner as in Example 2. An adhesive was obtained.

Phosphoric acid treated water resistant aluminum nitride [trade name; 283 parts by mass of HF-01A, an average particle diameter of 1.1 µm, a Mohs hardness of 8, a thermal conductivity of 200 W / m · K, manufactured by KK, and an ion trap agent [trade name; IXE-6107, a bismuth zirconium system, and Toagosei Co., Ltd. product 4.3 mass parts was used like Example 3, and the composition for film adhesives and the film adhesive were obtained.

Phosphoric acid treated water resistant aluminum nitride [trade name; 283 parts by mass of HF-01A, an average particle diameter of 1.1 µm, a Mohs hardness of 8, a thermal conductivity of 200 W / m · K, manufactured by KK, and an ion trap agent [trade name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] A composition for a film adhesive and a film adhesive were obtained in the same manner as in Example 3 except that 4.3 parts by mass were used.

Phosphoric acid treated water resistant aluminum nitride [trade name; 490 parts by mass of HF-01A, an average particle diameter of 1.1 µm, a Mohs hardness of 8, a thermal conductivity of 200 W / m · K, manufactured by KKK, and an ion trap agent [trade name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] A composition for a film adhesive and a film adhesive were obtained in the same manner as in Example 3 except that 7.4 parts by mass was used.

Phosphoric acid treated water resistant aluminum nitride [trade name; 169 parts by mass of HF-01A, an average particle diameter of 1.1 µm, a Mohs hardness of 8, a thermal conductivity of 200 W / m · K, manufactured by KKK, and an ion trap agent [trade name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] A composition for a film adhesive and a film adhesive were obtained in the same manner as in Example 3 except that 2.5 parts by mass were used.

Phosphoric acid treated water resistant aluminum nitride [trade name; 134 parts by mass of HF-01A, an average particle diameter of 1.1 µm, a Mohs hardness of 8, a thermal conductivity of 200 W / m · K, manufactured by KK, and an ion trap agent [trade name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] A composition for a film adhesive and a film adhesive were obtained in the same manner as in Example 3 except that 2.1 parts by mass were used.

(Comparative Example 1)

Water-resistant untreated aluminum nitride filler [brand name: HF-01A, average particle diameter 1.1μm, Mohs' hardness 8, thermal conductivity 200W / m * K, product made from KK Corporation] 273 mass parts instead of water-resistant untreated aluminum nitride filler [brand name: HF- 01, an average particle diameter of 1.1 μm, a Mohs hardness of 8, a thermal conductivity of 200 W / (m · K), manufactured by Kabushiki Shatokuyama Co., Ltd.] The composition for a film adhesive and the film adhesive were prepared in the same manner as in Example 1 except that 273 parts by mass were used. Got it.

(Comparative Example 2)

Spherical alumina filler [brand name: AX3-15R] instead of 273 mass parts of phosphoric acid water-resistant aluminum nitride [brand name: HF-01A, average particle diameter 1.1μm, Mohs hardness 8, thermal conductivity 200W / m * K, product made from KK Corporation] , Average particle diameter 3.0 μm, Mohs hardness 9, thermal conductivity 36 W / (m · K), manufactured by Shin-Nihon Seitetsu Material Co., Ltd.], 453 parts by mass except for using the composition and film for adhesive composition according to Example 1 A shape adhesive was obtained.

(Comparative Example 3)

Phosphoric acid water-resistant aluminum nitride [brand name: HF-01A, average particle diameter 1.1μm, Mohs hardness 8, thermal conductivity 200W / mK, product made from Kabuki Kaisha Tokuyama] Instead of 273 mass parts boron nitride filler [brand name: UHP-01, Average particle diameter 8.0 μm, Mohs hardness 2, thermal conductivity 60 W / mK, Showa Denko Co., Ltd.] 92 mass parts except using the composition and film adhesive composition similar to Example 1 except having used A shape adhesive was obtained.

(Comparative Example 4)

79 mass parts of phosphoric acid-treated water-resistant aluminum nitride (brand name: HF-01A, mean particle diameter 1.1 micrometers, Mohs' hardness 8, heat conductivity 200W / m * K, KK make), and an ion trap agent [brand name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] 1.2 mass parts was used, and the composition for film adhesives and the film adhesive were obtained like Example 8 except having used.

(Comparative Example 5)

605 mass parts of phosphoric acid-treated water-resistant aluminum nitride (brand name: HF-01A, average particle diameter 1.1 micrometers, Mohs' hardness 8, thermal conductivity 200W / m * K, the KKK make), and an ion trap agent [brand name; IXE-100, zirconium series, manufactured by Toagosei Co., Ltd.] A composition for a film adhesive and a film adhesive were obtained in the same manner as in Example 8 except that 9.0 parts by mass were used.

The obtained results are collectively shown in Tables 1 and 2 below.

In addition, the number which shows the compounding quantity of a material is a mass part.

From the said Tables 1 and 2, the following points are clear.

As shown in Examples 1-8, it contains an epoxy resin, an epoxy resin hardening | curing agent, a phenoxy resin, and an aluminum nitride filler, respectively, and content of an aluminum nitride filler is 30-60 volume with respect to the total amount of these resins and the said filler. %, Which satisfies all the properties of the film adhesive specified in the present invention, while suppressing generation of voids while maintaining high thermal conductivity, and excellent in corrosion resistance and blade friction resistance.

On the other hand, in the comparative example 1, compared with Examples 1 and 2, the value of extract water electrical conductivity was high and the corrosion property was inferior. This is presumed to be the result of the difference between the combination of the surface treating agent and the aluminum nitride acting significantly compared to the amount of ammonium ions generated during the bias HAST test.

On the other hand, in Comparative Examples 2 and 3 using spherical alumina and boron nitride without using an aluminum nitride filler, in Comparative Example 2 using spherical alumina, despite satisfying all the properties of the film adhesive specified in the present invention, Blade friction was poor. In addition, in Comparative Example 3 using boron nitride, voids were generated. This cause is assumed to be based on the fact that the boron nitride has a flaky shape, and therefore the melt viscosity after blending with the resin binder is more likely to be increased than the spherical shape.

In Comparative Example 4 in which the content of the aluminum nitride filler was less than 30% by volume with respect to the total amount of the epoxy resin, the epoxy resin curing agent, the phenoxy resin, and the aluminum nitride filler, the minimum melt viscosity and the thermal conductivity were low. As a result, when mounting the semiconductor chip provided with the film adhesive on the wiring board, the flaw defect of the film adhesive tends to occur easily, and the generated heat becomes difficult to be released to the outside of the package.

In contrast, in Comparative Example 5 in which the content of the aluminum nitride filler was greater than 60% by volume, the minimum melt viscosity and the electrical conductivity of the extract water were high, voids were generated, and the corrosiveness was also inferior.

Although the present invention has been described with its embodiments and examples, we do not intend to limit our invention in any detail of the description unless otherwise indicated, and contrary to the spirit and scope of the invention as indicated in the appended claims. We think that it should be interpreted widely without work.

This application claims the priority based on Japanese Patent Application No. 2016-51630 by which the patent application was carried out in Japan on March 15, 2016, This content is taken in here as a part of description of this specification.

1: semiconductor wafer
2: film-like adhesive layer
3: dicing tape
4: semiconductor chip
5: semiconductor chip with film shape adhesive
6: wiring board
7: bonding wire
8: sealing resin
9: semiconductor package

Claims (7)

As a composition for film adhesives containing an epoxy resin (A), an epoxy resin hardener (B), a phenoxy resin (C), an aluminum nitride filler (D), and a phosphate ester type surfactant, respectively,
Content of the said aluminum nitride filler (D) is 30-60 volume% with respect to the total amount of the said epoxy resin (A), the said epoxy resin hardener (B), the said phenoxy resin (C), and the said aluminum nitride filler (D). Is,
The compounding quantity of surfactant with respect to the said aluminum nitride filler (D) is 0.1-5.0 mass%,
As an additive of the composition for film adhesives, a phosphorus-boron type curing catalyst is included, and the phosphorus-boron type curing catalyst is tetraphenylphosphonium tetraphenylborate, or tetraphenylphosphonium tetra-p-triborate,
As for the said aluminum nitride filler (D), the surface oxide layer is given to the surface of the said filler, and the water-resistant surface treatment with a phosphoric acid or a phosphate compound is given,
When the film adhesive obtained by the said composition for film adhesives was heated up at the temperature increase rate of 5 degree-C / min at 25 degreeC, it reached the minimum melt viscosity of the range of 200-10000 Pa.s at 80 degreeC or more, and thermosetting Later, a thermal conductivity of 1.0W / mK or more gives a cured product, and the electrical conductivity of the extract water extracted in pure water at 121 ° C. 20 hours after thermosetting is 50 μS / cm or less, wherein the composition for film adhesive . The method of claim 1,
1.0-3.0 mass% of ion trapping agents chosen from a triazine thiol compound, a zirconium type compound, an antimony bismuth type compound, and a magnesium aluminum type compound with respect to the said aluminum nitride filler (D) for film adhesives Composition. The film adhesive obtained by the composition for film adhesives of Claim 1 or 2. The composition for film adhesives of Claim 1 or 2 is manufactured by coating and drying on the release-treated base film, The manufacturing method of the film adhesive characterized by the above-mentioned. A first step of providing a adhesive layer by thermocompression bonding the film adhesive and the dicing tape according to claim 3 on the back surface of the semiconductor wafer on which at least one semiconductor circuit is formed on the surface;
A second step of obtaining an adhesive layer-added semiconductor chip comprising the semiconductor wafer and the adhesive layer by dicing the semiconductor wafer and the adhesive layer simultaneously;
A third step of detaching the dicing tape from the adhesive layer and thermally compressing the adhesive layer addition semiconductor chip and the wiring substrate through the adhesive layer;
And a fourth step of thermosetting the adhesive layer. It is obtained by the manufacturing method of Claim 5, Comprising: The semiconductor package characterized by the above-mentioned. delete

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