TW201506117A - Thermosetting die bonding film, die bonding film attached with cutting sheet, and semiconductor device manufacturing method - Google Patents

Abstract

The present invention provides a thermosetting die bonding film with high thermal conductivity, a die bonding film attached with a cutting sheet using the thermosetting die bonding film, and a semiconductor device manufacturing method. This invention relates to a thermosetting die bonding film comprising thermally conductive particles; the aforementioned thermally conductive particles use a silane coupling agent for performing surface treatment; the content of said thermally conductive particles is 75 wt% or more with respect to the whole thermosetting die bonding film; the thermosetting die bonding film has a thermal conductivity of 1W/m.K or more after thermal curing.

Description

Thermosetting wafer bonding film, wafer bonded film with dicing sheet, and method of manufacturing semiconductor device

The present invention relates to a thermosetting wafer bonding film, a wafer bonding film with a dicing sheet, and a method of manufacturing a semiconductor device.

In recent years, as the speed of data processing of semiconductor devices has progressed, the amount of heat generated from semiconductor wafers has increased, and the design of semiconductor devices having heat dissipation has increased. Heat not only adversely affects the semiconductor device itself, but also causes various adverse effects on the electronic device body in which the semiconductor device is assembled. Various methods have been considered as packaging countermeasures for heat dissipation, and the most important thing is heat dissipation through a substrate such as a printed substrate or a lead fram.

Therefore, conventionally, an adhesive having high thermal conductivity has been used for adhesion between a substrate and a semiconductor wafer. Conventionally, as the adhesive, a silver paste having a high thermal conductivity among the adhesives has been used.

However, in recent years, due to the spread and high performance of smart phones and tablet computers, with the thinness and miniaturization of semiconductor devices, the silver paste has been difficult to assemble semiconductor devices.

Specifically, in the use of a smart phone or a tablet, a package using a semiconductor wafer having a small and thin wafer area is used. However, when it is desired to bond such a semiconductor wafer with a paste-like adhesive, various manufacturing problems occur as follows: since the semiconductor wafer is thin, the semiconductor wafer is broken or has a circuit surface on the semiconductor wafer. The adhesive is entangled, or the semiconductor wafer is tilted or the like. In addition, voids are easily generated in a process of bonding and curing a paste-like adhesive. Therefore, the gap generated between the semiconductor wafer and the substrate hinders heat dissipation, and thus it is impossible to exhibit defects such as thermal conductivity (heat dissipation) of the design.

On the other hand, a sheet-like wafer bonding film is known in the related art (see, for example, Patent Document 1). When such a wafer bonding film is used, damage of the wafer, entrapment of the adhesive, and tilt of the wafer can be performed. However, compared with the silver paste, the conventional wafer bonding film has a low thermal conductivity, and there is room for improvement in this respect.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-218571

In order to make the wafer bonding film highly thermally conductive, a method of filling a large amount of thermally conductive particles can be considered. However, since the thermally conductive particles are difficult to disperse in the resin, it is difficult to fill the thermally conductive particles in a large amount.

The first invention has been completed in view of the foregoing problems, and the present invention It is an object of the invention to provide a thermosetting wafer bonding film having high thermal conductivity, a wafer bonding film using a dicing sheet using a thermosetting wafer bonding film, and a method of manufacturing a semiconductor device.

The inventors of the present application have studied the thermosetting wafer bonding film in order to solve the above conventional problems. As a result, it has been found that the first invention can be completed by incorporating the thermally conductive particles in a large amount and improving the thermal conductivity.

According to a first aspect of the invention, there is provided a thermosetting wafer-bonding film comprising thermally conductive particles, wherein the thermally conductive particles are surface-treated with a decane coupling agent, and the content of the thermally conductive particles is substantially the same as that of the thermosetting wafer-bonding film. 75 wt% or more, the thermal conductivity of the thermosetting wafer bonding film after thermal curing is 1 W / m. K or more.

In the first aspect of the invention, since the thermally conductive particles surface-treated with the decane coupling agent are used, the dispersibility of the thermally conductive particles can be improved, and the thermally conductive particles can be filled in a large amount. Therefore, high thermal conductivity can be obtained.

The thermal conductivity of the above thermally conductive particles is preferably 12 W/m. K or more. Thereby, high thermal conductivity can be obtained.

Preferably, the decane coupling agent contains a hydrolyzable group, and the hydrolyzable group is a methoxy group and/or an ethoxy group.

It is preferable that the decane coupling agent contains an organic functional group, and the organic functional group contains at least one selected from the group consisting of an acryloyl group, a methacryl group, an epoxy group, and a phenylamine group.

It is preferred that the above decane coupling agent does not contain a primary amino group, a mercapto group or an isocyanate group.

Preferably, the melt viscosity at 130 ° C is 300 Pa. s below. Since the fluidity at a normal wafer bonding temperature (120 ° C to 130 ° C) is high, it is possible to follow the irregularities of the adherend such as a printed circuit board, and it is possible to suppress the occurrence of voids. Thereby, a semiconductor device having few voids and excellent heat dissipation properties can be obtained.

It is preferable that the thickness of the thermosetting wafer bonding film is 50 μm or less.

The first invention relates to a method of fabricating a semiconductor device, comprising the steps of: preparing the thermosetting wafer bonding film; and bonding the semiconductor wafer wafer to the adherend via the thermosetting wafer bonding film A step of.

The first invention relates to a wafer-bonding film with a dicing sheet on which a thermosetting type wafer bonding film is laminated on a dicing sheet, the dicing sheet being laminated with a binder layer on a substrate.

The first invention relates to a method of fabricating a semiconductor device, comprising the steps of: preparing a wafer bonding film with a dicing sheet; and using the thermosetting wafer bonding film and the semiconductor crystal of the wafer bonding film with the dicing sheet a step of bonding the back surface of the circle; cutting the semiconductor wafer together with the thermosetting wafer bonding film to form a wafer-shaped semiconductor wafer; and using the semiconductor wafer together with the thermosetting wafer bonding film a step of picking up a wafer-bonded film with a dicing sheet; and passing the above-described thermosetting wafer bonding film The step of bonding the semiconductor wafer to the adherend.

1‧‧‧Substrate

2‧‧‧Binder layer

2a‧‧‧corresponding to part 39

Other parts of 2b‧‧‧2a

3, 3'‧‧‧ wafer bonding film (thermosetting wafer bonding film)

3a‧‧‧Working part attachment

Parts other than 3b‧‧3a

4‧‧‧Semiconductor wafer

5‧‧‧Semiconductor wafer

6‧‧‧Adhesive

7‧‧‧bonding leads

8‧‧‧Encapsulation resin

10,12‧‧‧ wafer bonded film with cut sheets

11‧‧‧Cut slices

Fig. 1 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to the first embodiment.

2 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a modification of the first embodiment.

3 is a schematic cross-sectional view for explaining a method of manufacturing the semiconductor device of the first embodiment.

Fig. 4 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a second embodiment.

Fig. 5 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a modification of the second embodiment.

Fig. 6 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a third embodiment.

Fig. 7 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a modification of the third embodiment.

Fig. 8 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a fourth embodiment.

Fig. 9 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a modification of the fourth embodiment.

Fig. 10 is a schematic cross-sectional view showing a wafer bonding film with a dicing sheet according to a fifth embodiment.

Fig. 11 is a view showing a crystal of a cut sheet according to a modification of the fifth embodiment; A schematic cross-sectional view of a sheet-joining film.

Fig. 12 is a schematic cross-sectional view for explaining a method of manufacturing the semiconductor device of the fifth embodiment.

<<First invention>>

Hereinafter, the first invention will be described in detail with reference to Embodiment 1, but the first invention is not limited thereto.

[Embodiment 1] (wafer bonding film with cut sheet)

Hereinafter, a thermosetting wafer bonding film (hereinafter also referred to as "wafer bonding film") of the first embodiment and a wafer bonding film with a dicing sheet will be described. In the wafer bonding film of the dicing sheet described below, the wafer bonding film in the state in which the dicing sheet is not bonded is exemplified. Therefore, the wafer bonding film with the dicing sheet will be described below, and the wafer bonding film will be described with respect to the wafer bonding film.

As shown in FIG. 1, the wafer bonding film 10 with a dicing sheet has a configuration in which a thermosetting wafer bonding film 3 is laminated on a dicing sheet 11. The dicing sheet 11 is formed by laminating a binder layer 2 on a substrate 1, and the wafer bonding film 3 is provided on the binder layer 2. The wafer bonding film 3 is provided with a workpiece attaching portion 3a for attaching a work and a peripheral portion 3b disposed at a periphery of the workpiece attaching portion 3a. As shown in Figure 2, the modification It is possible to provide the wafer bonding film 12 with the wafer bonding film 3' attached to the dicing sheet only at the workpiece attaching portion.

The base material 1 has ultraviolet light transmittance and is a strength matrix of the wafer bonding films 10 and 12 to which the dicing sheets are attached. Examples thereof include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopoly polypropylene, and polybutylene. Polyolefins such as olefins and polymethylpentene; ethylene-vinyl acetate copolymers, ionic polymer resins, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylates (random, alternating) copolymers , ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate and other polyesters; polycarbonate, polyimine, polyether Ether ketone, polyimide, polyether quinone, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aramid (paper), glass, glass cloth, fluororesin, polyvinyl chloride , polyvinylidene chloride, cellulose resin, epoxy resin, metal (foil), paper, and the like.

Moreover, the material of the base material 1 is a polymer, such as a bridge|crosslinking body of the said resin. The plastic film may be used without stretching, or a plastic film subjected to uniaxial or biaxial stretching treatment may be used as needed. When the resin sheet to which heat shrinkability is imparted by the stretching treatment or the like is used, the adhesion of the substrate 1 to the wafer bonding film 3, 3' can be reduced by heat shrinking after the dicing. The ease of recycling semiconductor wafers is achieved.

In order to improve adhesion to adjacent layers, retention, and the like, the surface of the substrate 1 may be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, Chemical treatment or physical treatment such as flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, or coating treatment using a primer (for example, an adhesive described later). The substrate 1 may be appropriately selected from the same or different types of substrates, and if necessary, a plurality of substrates may be blended.

The thickness of the substrate 1 is not particularly limited and can be appropriately determined, and is usually about 5 to 200 μm.

The adhesive for forming the adhesive layer 2 is not particularly limited, and for example, a usual pressure-sensitive adhesive such as an acrylic adhesive or a rubber adhesive can be used. The pressure sensitive adhesive is preferably acrylic acid based on an acrylic polymer from the viewpoints of cleaning and cleaning properties of an organic solvent such as ultrapure water or alcohol from a semiconductor component such as a semiconductor wafer or glass. Type of binder.

Examples of the acrylic polymer include alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, and pentane). Ester, isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, decyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, thirteen An alkyl group such as an alkyl ester, a tetradecyl ester, a hexadecyl ester, an octadecyl ester or an eicosyl ester having a carbon number of 1 to 30, particularly a linear or branched carbon number of 4 to 18. One or two or more kinds of acrylic polymers such as a chain alkyl ester (such as a chain alkyl ester) and a cycloalkyl (meth)acrylate (for example, a cyclopentyl ester or a cyclohexyl ester) are used as a monomer component. The (meth) acrylate means an acrylate and/or a methacrylate, and in the present specification, it has the same meaning as all of (meth).

For the purpose of reforming cohesion, heat resistance, etc., the aforementioned acrylic polymer A unit corresponding to other monomer components copolymerizable with the aforementioned alkyl (meth) acrylate or cycloalkyl ester may be contained as needed. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. Monomer of carboxyl group; anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxyl (meth)acrylate Butyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate a hydroxyl group-containing monomer such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropane a sulfonic acid group-containing monomer such as sulfonic acid, (meth) acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; 2-hydroxyethyl propylene a phosphate group-containing monomer such as hydrazine phosphate; acrylamide, acrylonitrile, or the like. These monomer components which can be copolymerized may be used alone or in combination of two or more. The amount of these copolymerizable monomers is preferably 40% by weight or less based on the total of the monomer components.

Further, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as needed in order to carry out crosslinking. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and new Pentandiol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol six (a) Acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer to be used is preferably 30% by weight or less based on the total of the monomer components.

The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization may be carried out in any form such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization. It is preferable that the content of the low molecular weight substance is small from the viewpoint of preventing contamination of the cleaned adherend or the like. From this point of view, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 to 3,000,000, and particularly preferably 300,000 to 1,000,000.

Further, in the above-mentioned binder, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent can be suitably used. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine crosslinking agent to react. When an external crosslinking agent is used, the amount thereof is appropriately determined depending on the balance with the base polymer to be crosslinked, and the use as a binder. It is usually preferably 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, in the binder, in addition to the above-mentioned components, additives such as various conventionally known various tackifiers and anti-aging agents may be used as needed.

The adhesive layer 2 can be formed using a radiation curable adhesive. put The radiation-curable adhesive can increase the degree of crosslinking by irradiating radiation such as ultraviolet rays, and the adhesion can be easily lowered by only the portion 2a corresponding to the attached portion of the adhesive layer 2 shown in FIG. The radiation can be irradiated, and the difference in adhesion to the other portion 2b can be set.

Further, by bonding the radiation-curable adhesive layer 2 to the wafer bonding film 3' shown in Fig. 2, the portion 2a in which the adhesion is remarkably lowered can be easily formed. Since the wafer bonding film 3' is attached to the aforementioned portion 2a which is cured and has a reduced adhesive force, the interface between the aforementioned portion 2a of the adhesive layer 2 and the wafer bonding film 3' has a property of being easily peeled off at the time of picking up. On the other hand, the portion where the radiation is not irradiated has a sufficient adhesive force to form the aforementioned portion 2b. Irradiating the adhesive layer with radiation can be performed after cutting and before picking up.

As described above, in the adhesive layer 2 of the wafer-bonding film 10 with a dicing sheet shown in Fig. 1, the aforementioned portion 2b formed of an uncured radiation-curable adhesive is bonded to the wafer bonding film 3, and the cutting can be ensured. The retention of time. In this manner, the radiation-curable adhesive can support the wafer bonding film 3 for fixing a wafer-like workpiece (a semiconductor wafer or the like) to an adherend such as a substrate in a well-balanced adhesion/peeling. In the adhesive layer 2 of the wafer-bonding film 11 with a dicing sheet shown in Fig. 2, the aforementioned portion 2b can fix the wafer ring.

The radiation-curable adhesive is not particularly limited as long as it has a radiation-curable functional group such as a carbon-carbon double bond and exhibits adhesiveness. The radiation-curable adhesive may, for example, be formulated with a radiation-fixing agent in a usual pressure-sensitive adhesive such as the above-mentioned acrylic adhesive or rubber adhesive. An additive radiation curable adhesive comprising a monomer component and an oligomer component.

Examples of the radiation-curable monomer component to be blended include a urethane oligomer, a urethane (meth) acrylate, a trimethylolpropane tri(meth) acrylate, and a tetrahydroxy group. Methyl methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is from 100 to 30,000. The range around is appropriate. The amount of the radiation-curable monomer component and the oligomer component can be appropriately determined depending on the type of the binder layer, and the amount of adhesion of the binder layer can be appropriately reduced. In general, it is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the base polymer such as an acrylic polymer constituting the binder.

Further, in addition to the above-described additive-type radiation-curable adhesive, the radiation-curable adhesive may be one which has a carbon-carbon double bond in a polymer side chain or a main chain or at a main chain terminal. An intrinsic radiation-curing adhesive that acts as a base polymer. Since the intrinsic type radiation-curable adhesive does not need to contain or contain a large amount of an oligomer component or the like which is a low molecular component, the oligomer component or the like does not move over the binder layer with time, and a layer structure can be formed stably. The adhesive layer is preferred.

The aforementioned base polymer having a carbon-carbon double bond may be not particularly limited A polymer having a carbon-carbon double bond and having adhesiveness is used. Such a base polymer preferably has an acrylic polymer as a basic skeleton. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

The method of introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be employed. From the viewpoint of molecular design, it is easy to introduce a carbon-carbon double bond into the polymer side chain. For example, a method in which an acrylic polymer is copolymerized with a monomer having a functional group, and then a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is maintained in maintaining a carbon-carbon double bond A method of performing a polycondensation or an addition reaction in a state of radiation curability.

Examples of the combination of these functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is suitable from the viewpoint of easiness of tracking the reaction. Further, as long as a combination of these functional groups is used to form a combination of an acrylic polymer having the aforementioned carbon-carbon double bond, the functional group may be on either side of the acrylic polymer and the aforementioned compound, in the aforementioned In a preferred combination, the case where the acrylic polymer has a hydroxyl group and the aforementioned compound has an isocyanate group is suitable. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate, 2-methyl propylene methoxyethyl isocyanate, m-isopropenyl-α, α-dimethyl benzyl. Isocyanate and the like. Further, as the acrylic polymer, the above-exemplified hydroxyl group-containing monomer, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl group can be used. A polymer obtained by copolymerization of an ether compound or the like.

The intrinsic radiation-curable adhesive may be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or may be prepared by disposing the radiation-curable monomer to such an extent that the properties are not deteriorated. Ingredients, oligomer components. The radiation curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer.

The radiation curable adhesive contains a photopolymerization initiator when it is cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, and 2 An α-keto alcohol compound such as methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenone-based compound such as 2,2-diethoxyacetophenone or 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropan-1-one; benzene a benzoin ether compound such as acetoin ethyl ether, benzoin isopropyl ether, fennel aceton methyl ether; a ketal compound such as benzyl dimethyl ketal; an aromatic compound such as 2-naphthalene sulfonium chloride a sulfonium chloride compound; a photoactive lanthanide compound such as 1-benzophenone-1,1-propanediol-2-(O-ethoxycarbonyl)anthracene; benzophenone, benzhydrylbenzoic acid, 3,3 a benzophenone compound such as '-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethyl Thiophenone compounds such as thioxanthone, isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone ; camphor; haloketone; sulfhydryl phosphine oxide Acyl phosphonate and the like. The amount of the photopolymerization initiator is adjusted based on the base polymerization such as the acrylic polymer constituting the binder. 100 parts by weight of the substance is, for example, about 0.05 to 20 parts by weight.

In addition, the radiation-curable adhesive, for example, includes an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group as disclosed in JP-A-60-196956 A rubber-based adhesive, an acrylic adhesive, or the like of a photopolymerization initiator such as a polymerizable compound, a carbonyl compound, an organic sulfur compound, a peroxide, an amine or a phosphonium salt compound.

The radiation-curable adhesive layer 2 may contain a compound that is colored by radiation irradiation, if necessary. By including the compound colored by radiation irradiation in the adhesive layer 2, only the portion irradiated with radiation can be colored. That is, the portion 2a corresponding to the workpiece attaching portion 3a shown in Fig. 1 can be colored. Therefore, it is possible to directly determine whether or not the adhesive layer 2 has been irradiated with radiation by visual observation, and it is easy to recognize the workpiece attaching portion 3a, and it is easy to attach the workpiece. Further, when a semiconductor wafer is detected by a photo sensor or the like, the detection accuracy is improved, and an erroneous operation does not occur at the time of picking up the semiconductor wafer.

A compound colored by radiation irradiation is a colorless or light color before irradiation with radiation, but becomes a colored compound by radiation irradiation. A preferred specific example of the compound is a leuco dye. The leuco dye is preferably a conventional triphenylmethane system, a fluoran (Fluoran) system, a phenothiazine system, a gold amine system or a spiropyran. Specifically, 3-[N-(p-tolylamino)]-7-anilinofluoran, 3-[N-(p-tolyl)-N-methylamino]-7-aniline can be exemplified. , fluorinated, 3-[N-(p-tolyl)-N-ethylamino]-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilino Fluorane, crystal violet lactone, 4,4',4"-tris(dimethylamino)triphenylmethanol, 4,4',4"-tris(dimethylamino)triphenylmethane, etc. .

The coloring agent which is preferably used together with these leuco dyes may be an electron acceptor such as an initial polymer of a phenol resin used in the prior art, an aromatic carboxylic acid derivative or an activated clay, and a color tone may be changed. Hereinafter, various known developers can also be used in combination.

Such a compound colored by radiation irradiation may be contained in a radiation-curable adhesive once dissolved in an organic solvent or the like, or may be made into a fine powder and contained in the adhesive in a ratio of the compound used in the adhesive layer. 2 is 10% by weight or less, preferably 0.01 to 10% by weight, and more preferably 0.5 to 5% by weight. When the ratio of the compound exceeds 10% by weight, the radiation applied to the binder layer 2 is excessively absorbed by the compound. Therefore, the curing of the portion 2a of the binder layer 2 is insufficient, and the adhesive strength may not be sufficiently lowered. On the other hand, in order to sufficiently colorize it, it is preferable to make the ratio of this compound into 0.01 weight% or more.

When the adhesive layer 2 is formed by the radiation-curable adhesive, a part of the adhesive layer 2 can be irradiated with radiation so that the adhesive force of the portion 2a in the adhesive layer 2 is less than the adhesive force of the other portion 2b.

In the method of forming the above-mentioned portion 2a in the above-mentioned adhesive layer 2, a method in which the radiation-curable adhesive layer 2 is formed on the support substrate 1 and the portion 2a is partially irradiated with radiation to be cured is exemplified. The local radiation irradiation can be performed via a photomask formed with a pattern corresponding to the portion 3b or the like other than the workpiece attaching portion 3a. Further, a method in which a spot is irradiated with ultraviolet rays to be cured is exemplified. Radiation curing The formation of the type of adhesive layer 2 can be carried out by transferring the adhesive layer 2 provided on the separator to the support substrate 1. Local radiation curing can also be performed on the radiation-curable adhesive layer 2 provided on the separator.

Further, when the adhesive layer 2 is formed by the radiation-curable adhesive, a support substrate which shields all or a part of a portion other than the portion corresponding to the workpiece attachment portion 3a of at least one side of the support substrate 1 is used. 1. After the radiation-curable adhesive layer 2 is formed, the radiation is irradiated to cure the portion corresponding to the workpiece attaching portion 3a, so that the portion 2a in which the adhesive force is lowered can be formed. The light-shielding material can be produced by printing, vapor-depositing, or the like on a material that can be a photomask on a support film. According to this manufacturing method, the wafer bonding film 10 with the dicing sheet can be efficiently manufactured.

When radiation is irradiated, when curing is inhibited by oxygen, it is preferable to isolate oxygen (air) from the surface of the radiation-curable adhesive layer 2 by a certain method. For example, a method of covering the surface of the pressure-sensitive adhesive layer 2 with a separator and a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere may be mentioned.

The thickness of the adhesive layer 2 is not particularly limited, and is preferably about 1 to 50 μm from the viewpoint of preventing the wafer cut surface from being damaged or the adhesion maintaining layer. It is preferably 2 to 30 μm, and more preferably 5 to 25 μm.

The melt adhesion at 130 ° C of the wafer bonding film 3, 3' is preferably 300 Pa. Below s, more preferably 280Pa. s below, and more preferably 250Pa. s below. 300Pa. Below s, at the usual wafer bonding temperature (120 ° C ~ The fluidity at 130 ° C) is high, and it is possible to follow the irregularities of the adherend such as a printed circuit board, and it is possible to suppress the occurrence of voids. In addition, the melt viscosity at 130 ° C is preferably 10 Pa. Above s, more preferably 20Pa. More than s, and more preferably 50Pa. s above. 10Pa. When s or more, the shape of the film can be maintained.

The melt viscosity at 130 ° C is a value obtained by setting the shear rate to 5 sec ^-1 as a measurement condition.

The melt viscosity at 130 ° C of the wafer bonded films 3, 3' can be controlled by the average particle diameter of the thermally conductive particles, the softening point of the epoxy resin, the softening point of the phenol resin, and the like. For example, by setting the average particle diameter of the thermally conductive particles to be large, lowering the softening point of the epoxy resin, and lowering the softening point of the phenol resin, the melt viscosity at 130 ° C can be lowered.

The thermal conductivity of the wafer bonding film 3, 3' after heat curing is 1 W/m. K or more, preferably 1.2 W/m. K or more, more preferably 1.5W/m. K or more. The thermal conductivity after heat curing is 1W/m. Since K is more than the above, the semiconductor device manufactured using the wafer bonding films 3 and 3' is excellent in heat dissipation. The higher the thermal conductivity of the wafer bonding film 3, 3' after heat curing, the better, but for example, 20 W/m. Below K.

The "thermal conductivity after heat curing" means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

The wafer bonded films 3, 3' include thermally conductive particles which have been surface-treated (pretreated) with a decane coupling agent. The surface-treated thermally conductive particles are excellent in dispersibility and can be filled in a large amount in the die-bonding films 3 and 3'.

The decane coupling agent preferably contains a halogen atom, a hydrolyzable group, and an organic group. A functional decane coupling agent.

The hydrolyzable group is bonded to a ruthenium atom.

Examples of the hydrolyzable group include a methoxy group and an ethoxy group. Among them, a methoxy group is preferred because it has a high hydrolysis rate and is easy to handle.

From the viewpoint of being able to crosslink the thermally conductive particles and crosslinking the decane coupling agents, and even if the crosslinking points on the surface of the thermally conductive particles are small, the thermal conductive particles can be surface-treated with a decane coupling agent, decane coupling The number of the hydrolyzable groups in the agent is preferably 2 to 3, more preferably 3.

The organic functional group is bonded to the ruthenium atom.

The organic functional group may, for example, be an organic functional group including an acryloyl group, a methacryl group, an epoxy group, or a phenylamino group (-NH-Ph). Among them, the thermal conductive particles which are not reactive with the epoxy resin and have excellent storage stability are preferably propylene groups.

When a functional group having high reactivity with an epoxy group is formed, it reacts with an epoxy resin, and thus the storage stability and fluidity are lowered. From the viewpoint of suppressing the decrease in fluidity, the organic functional group is preferably one which does not contain a primary amino group, a mercapto group or an isocyanate group.

The number of the organic functional groups in the decane coupling agent is preferably one. Since the ruthenium atom forms four bonds, the amount of the hydrolysis group may be insufficient when the organic functional group is plural.

The decane coupling agent may further comprise an alkyl group bonded to a ruthenium atom. By including the alkyl group in the decane coupling agent, the reactivity can be made lower than that of the methacryl oxime group, and the variation in the surface treatment caused by the abrupt reaction can be prevented. alkyl The base may be a methyl group, a dimethyl group or the like. Among them, a methyl group is preferred.

The decane coupling agent, specifically, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-epoxypropyl Oxypropyl propyl triethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, dimethyl dimethoxy Base decane, dimethyl diethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, N-phenyl-3-amine Propyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropane Methyldiethoxy decane, 3-methacryloxypropyltriethoxydecane, and the like.

The method of treating the thermally conductive particles with a decane coupling agent is not particularly limited, and examples thereof include a wet method in which a thermally conductive particle and a decane coupling agent are mixed in a solvent, and coupling of a thermally conductive particle and a decane in a gas phase. Dry method for treating the agent.

The treatment amount of the decane coupling agent is not particularly limited, and it is preferred to treat 0.05 to 5 parts by weight of the decane coupling agent with respect to 100 parts by weight of the thermally conductive particles.

The thermal conductivity of the thermally conductive particles is preferably 12 W/m. K or more, more preferably 20W/m. K or more. The upper limit of the thermal conductivity of the thermally conductive particles is not particularly limited, and is, for example, 50 W/m. Below K, preferably 30 W/m. Below K.

The thermal conductivity of the thermally conductive particles can be estimated from the crystal structure of the thermally conductive particles obtained by X-ray structural analysis.

The average particle diameter of the thermally conductive particles is preferably 1 μm or more, and more preferably 1.5 μm or more. Since it is 1 μm or more, the fluidity at 120 ° C to 130 ° C can be improved. Further, the average particle diameter of the thermally conductive particles is preferably 10 μm or less, more preferably 8 μm or less. Since it is 10 μm or less, good film moldability can be obtained.

The average particle diameter of the thermally conductive particles can be measured by the method described in the examples.

In the particle size distribution of the thermally conductive particles, it is preferred to have two or more peaks. Specifically, it is preferred that a first peak exists in a particle diameter range of 0.2 to 0.8 μm, and a second peak exists in a particle diameter range of 3 to 15 μm. Thereby, the thermally conductive particles forming the first peak can be filled between the thermally conductive particles forming the second peak (in the gap), so that the thermally conductive particles can be filled in a large amount.

When the particle diameter of the first peak is less than 0.2 μm, the viscosity of the die-bonding films 3 and 3' tends to be high, and the unevenness of the adherend tends not to follow. When the particle diameter of the first peak exceeds 0.8 μm, a large amount of filling of the thermally conductive particles tends to be difficult.

Further, when the particle diameter of the second peak is less than 3 μm, it tends to be difficult to form a large amount of the thermally conductive particles. Further, the viscosity of the wafer bonding films 3, 3' tends to be too high to follow the irregularities of the adherend. When the particle diameter of the second peak exceeds 15 μm, it becomes difficult to form a thin film of the die-bonding films 3 and 3'.

The second peak is more preferably present in the particle size range of 4 to 8 μm.

In the particle size distribution of the thermally conductive particles, two or more peaks may be present, and two or more types of thermally conductive particles having different average particle diameters may be blended.

The shape of the thermally conductive particles is not particularly limited, and for example, flake, needle, filament, spherical, or scaly particles may be used, and particles having a sphericity of 0.9 or more are preferable, and more preferably 0.95 or more. Thereby, the contact area of the thermally conductive particles and the resin can be made small, and the fluidity at 120 ° C to 130 ° C can be improved. The closer the sphericity is to 1, the closer it is to the true sphere.

The sphericity of the thermally conductive particles can be measured by the following method.

Determination of sphericity

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. A photograph was taken of the obtained ash by SEM (Electronic Scanning Microscope), and the sphericity was calculated from the area and the circumference of the observed particles by the following formula. The sphericity was measured for 100 particles using an image processing apparatus (Sysmex Corporation: FPIA-3000).

(sphericity) = {4π × (area) ÷ (circumference) ² }

From the viewpoint of easily obtaining particles having high thermal conductivity and high sphericity, the thermally conductive particles are preferably alumina particles (thermal conductivity: 36 W/m.K) and zinc oxide particles (thermal conductivity: 54 W/m. K). ), aluminum nitride particles (thermal conductivity: 150 W/m. K), tantalum nitride particles (thermal conductivity: 27 W/m. K), niobium carbide particles (thermal conductivity: 200 W/m. K), magnesium oxide particles ( Thermal conductivity: 59 W/m.K), boron nitride particles (thermal conductivity: 60 W/m. K), and the like. In particular, the alumina particles have a high thermal conductivity and are preferred from the viewpoints of dispersibility and ease of availability. Further, since the boron nitride particles have a higher thermal conductivity, they can be suitably used.

The content of the thermally conductive particles is based on the entire wafer bonding film 3, 3' 75 wt% or more, preferably 80 wt% or more, more preferably 85 wt% or more. Since it is 75% by weight or more, the semiconductor device manufactured using the wafer bonding films 3, 3' is excellent in heat dissipation. In addition, the content of the thermally conductive particles is preferably as large as possible, but is, for example, 93% by weight or less from the viewpoint of film formability.

The die-bonding films 3, 3' preferably contain a resin component such as a thermosetting resin or a thermoplastic resin.

Examples of the thermosetting resin include a phenolic resin, an amine-based resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. Particularly preferred is an epoxy resin containing less ionic impurities such as etching semiconductor wafers. Further, as the curing agent for the epoxy resin, a phenol resin is preferable.

The epoxy resin is not particularly limited as long as it is generally used as a binder for wafer bonding, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol can be used. Type A, bisphenol AF type, biphenyl type, naphthalene type, hydrazine type, phenol novolac type, o-cresol novolak type, trihydroxyphenylmethane type, tetrakis(phenylhydroxy)ethane (Tetraphenylolethane) type, etc. A difunctional epoxy resin or a polyfunctional epoxy resin; or an epoxy resin such as an intramethylene urea type, a triglycidyl isocyanurate type or a glycidyl amine type. They may be used singly or in combination of two or more. Among them, bisphenol A type epoxy resin is preferable because it is liquid at room temperature and thus can impart flexibility to the die bond films 3 and 3' and can prevent the wafer bonding films 3 and 3' from being easily broken. .

From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, an epoxy resin which is liquid at room temperature is preferred.

In this specification, liquid means that the viscosity at 25 ° C is less than 5000 Pa. s. The viscosity can be measured using the model HAAKE Roto VISCO1 manufactured by Thermo Fisher Scientific K.K.

From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, the softening point of the epoxy resin is preferably 100 ° C or lower, more preferably 80 ° C or lower. More preferably, it is 70 ° C or less.

The softening point of the epoxy resin can be measured by the ring and ball method prescribed in JIS K 7234-1986.

Further, the phenol resin is used as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butylphenol novolak resin, and a nonylphenol novolac resin. A novolak type phenol resin such as a resin; a polyoxystyrene such as a resol type phenol resin or polyoxy oxy styrene; and the like. These may be used alone or in combination of two or more. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferred. This is because the connection reliability of the semiconductor device can be improved. Further, the reason why the heat conductivity is high and the rigidity is high, and the heat conductivity is preferably a phenol resin having a biphenyl aralkyl skeleton.

The softening point of the phenol resin is preferably 100 ° C or lower, more preferably 80 ° C or lower from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The softening point of the phenol resin can be measured by the ring and ball method prescribed in JIS K 6910-2007.

The blending ratio of the epoxy resin to the phenol resin is, for example, formulated such that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitably, it is 0.8 to 1.2 equivalents. In other words, when the blending ratio of the two is out of the above range, a sufficient curing reaction is not performed, and the properties of the cured epoxy resin are likely to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutadiene. Resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon, 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET, PBT, polyamidoguanidine Imine resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is less ionic impurities, has high heat resistance, and can secure the reliability of a semiconductor wafer is particularly preferable.

The acrylic resin is not particularly limited, and one or more of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18, may be mentioned as a component. Polymer (acrylic copolymer) and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a cyclohexyl group, and a 2-ethyl group. Hexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl, Or dodecyl and the like.

Further, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, and acrylic acid. a carboxyl group-containing monomer such as carboxypentyl ester, itaconic acid, maleic acid, fumaric acid or crotonic acid; an anhydride monomer such as maleic anhydride or itaconic anhydride; and 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate a hydroxyl group-containing monomer such as 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)methyl acrylate; styrenesulfonic acid, Allylsulfonic acid, 2-(meth)acrylamidoxime-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryl a sulfonic acid group-containing monomer such as decyl naphthalenesulfonic acid; or a phosphate group-containing monomer such as 2-hydroxyethyl propylene decyl phosphate.

The content of the resin component is preferably 7% by weight or more based on the entire wafer bonding film 3, 3'. The content of the resin component is preferably 25% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less based on the total of the wafer bonding films 3 and 3'.

The blending ratio of the thermosetting resin in the resin component (the total amount of the thermosetting resin and the thermoplastic resin) is not particularly limited as long as the wafer bonding films 3 and 3' exhibit a function as a thermosetting type when heated under predetermined conditions. From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, it is preferably in the range of 75 to 99% by weight, more preferably in the range of 85 to 98% by weight.

The blending ratio of the thermoplastic resin in the resin component is preferably in the range of 1 to 25% by weight, more preferably 2 to 15% by weight, from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The wafer bonding films 3, 3' preferably contain a curing catalyst. Thereby, thermal curing of the epoxy resin and a curing agent such as a phenol resin can be promoted. The curing catalyst is not particularly limited, and examples thereof include tetraphenylboron tetraphenylphosphonium (trade name; TPP-K), tetrakis(p-tolylboron)tetraphenylphosphonium (trade name; TPP-MK), and triphenylene. Phosphorus-boron-based curing catalysts such as phosphine triphenylborane (trade name; TPP-S) (both manufactured by Beixing Chemical Industry Co., Ltd.). Among them, when an epoxy resin and a phenol resin are used in combination, tetrakis(p-tolylboron)tetraphenylphosphonium is preferred from the viewpoint of high latent property and excellent storage stability at room temperature.

The content of the curing catalyst can be appropriately set, and is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermosetting resin.

When the wafer bonding films 3 and 3' are crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer is added as a crosslinking agent at the time of production. Just fine. Thereby, the adhesive property at a high temperature can be improved, and the heat resistance can be improved.

As the crosslinking agent, a conventionally known crosslinking agent can be used. More preferably, it is preferably a polyisocyanate compound such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, or an adduct of a polyhydric alcohol and a diisocyanate. The amount of the crosslinking agent to be added is usually preferably 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. When the amount of the crosslinking agent is more than 7 parts by weight, the adhesive strength is lowered, which is not preferable. On the other hand, when it is less than 0.05 part by weight, the cohesive force is not reached, which is not preferable. Further, together with such a polyisocyanate compound, an epoxy resin or the like may be contained together as needed. Other polyfunctional compounds.

Further, in the wafer bonding films 3, 3', a filler other than the thermally conductive particles can be appropriately blended depending on the application. The formulation of the filler can adjust the modulus of elasticity and the like. The filler may be exemplified by an inorganic filler and an organic filler. The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, aluminum borate whisker, crystalline cerium oxide, and amorphous cerium oxide. These may be used alone or in combination of two or more.

In the wafer bonding films 3, 3', in addition to the filler, other additives may be appropriately formulated as needed. Examples of other additives include a flame retardant, a decane coupling agent, an ion trapping agent, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These may be used alone or in combination of two or more. Examples of the decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropane. Methyl diethoxy decane, and the like. These compounds may be used singly or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and barium hydroxide. These may be used alone or in combination of two or more.

The laminated structure of the die-bonding films 3 and 3' is not particularly limited, and examples thereof include a structure formed only of a single layer of an adhesive layer, a multilayer structure in which an adhesive layer is formed on one surface or both surfaces of a core material, and the like. . The core material may, for example, be a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a glass fiber. A resin substrate, a ruthenium substrate, or a glass substrate reinforced with a plastic non-woven fabric.

The thickness of the wafer bonded films 3, 3' (the total thickness in the case of the laminate) is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. Further, the thickness of the die-bonding films 3, 3' is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less.

With respect to the substrate 1, the adhesive layer 2, and the die-bonding films 3, 3', in order to prevent static electricity generated during adhesion and peeling, or to cause destruction of the semiconductor wafer or the like, the circuit may be destroyed. The wafer bonding films 10 and 12 with the dicing sheets have an antistatic function. The antistatic function can be carried out by a method of adding an antistatic agent or a conductive material to the substrate 1, the adhesive layer 2, the die bonding films 3, 3', and attaching the substrate 1 to the substrate 1 by an appropriate method. A conductive layer made of a charge transfer complex, a metal film, or the like. Among these methods, it is preferred that the impurity ions which are likely to deteriorate the semiconductor wafer are not generated. The conductive material (conductive filler) to be added for the purpose of imparting conductivity, conductivity, and the like may be a spherical, needle-like or sheet-like metal powder such as silver, aluminum, gold, copper, nickel or a conductive alloy. , amorphous carbon black, graphite, etc.

The wafer bonding films 3, 3' of the wafer-bonding films 10, 12 with the dicing sheets are preferably protected by a separator (not shown). The separator has a function of providing a protective material for protecting the wafer bonding films 3, 3'. Further, the separator can be further used as a support substrate when the wafer bonding films 3, 3' are transferred to the adhesive layer 2. The separator is peeled off when the workpiece is bonded to the wafer bonding films 3, 3' of the wafer bonding films 10, 12 to which the dicing sheets are attached. Polyethylene terephthalate can also be used as the separator. (PET), polyethylene, polypropylene, a plastic film or paper which has been surface-coated with a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate release agent.

The wafer bonded films 10 and 12 of the dicing sheet according to the present embodiment can be produced, for example, as follows.

First, the substrate 1 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calender film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T die extrusion method, a coextrusion method, a dry lamination method, and the like. .

Next, after applying a binder to the substrate 1 and forming a coating film with the solution, the coating film is dried under predetermined conditions (heat-crosslinked as necessary) to form the binder layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen printing coating, gravure coating, and the like. Further, the drying conditions are carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Alternatively, the coating film may be formed by applying a binder to the separator and forming a coating film, and then drying the coating film under the drying conditions to form the binder layer 2. Thereafter, the adhesive layer 2 is bonded to the substrate 1 together with the separator. Thus, the cut sheet 11 is produced.

The wafer bonding films 3, 3' can be produced, for example, as follows.

First, a binder composition which is a material for forming the wafer bonding films 3, 3' is produced. In the adhesive composition, as described above, a thermosetting resin, a thermoplastic resin, thermal conductive particles, and various other additives are blended as needed. Usually, the adhesive composition is used in a state of a solution dissolved in a solvent or a state of a dispersion dispersed in a solvent (hereinafter, a solution form) The state of the dispersion is also included in the state).

Next, the adhesive composition solution is applied onto the substrate separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form an adhesive layer. The coating method is not particularly limited, and examples thereof include roll coating, screen printing coating, gravure coating, and the like. Further, the drying conditions are carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Further, after the binder composition solution is applied onto the separator to form a coating film, the coating film is dried under the drying conditions to form an adhesive layer. Thereafter, the adhesive layer is attached to the substrate separator together with the separator.

Next, the separator is peeled off from the dicing sheet 11 and the adhesive layer, and the adhesive layer and the adhesive layer 2 are bonded to each other so that the adhesive layer 2 is a bonding surface. The bonding can be performed, for example, by crimping. In this case, the lamination temperature is not particularly limited, and is, for example, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.1 to 20 kgf/cm, more preferably 1 to 10 kgf/cm. Next, the substrate separator on the adhesive layer was peeled off to obtain the wafer bonded films 10 and 12 of the cut sheet of the present embodiment.

(Method of Manufacturing Semiconductor Device)

The method of manufacturing the semiconductor device of the first embodiment and the method of manufacturing the semiconductor device of the embodiment 1-2 will be described as a method of manufacturing the semiconductor device according to the first embodiment.

The method of manufacturing a semiconductor device according to Embodiment 1-1 includes the following steps a step of preparing the aforementioned thermosetting wafer bonding film; and a wafer bonding step of bonding the semiconductor wafer to the adherend via the aforementioned thermosetting wafer bonding film.

Further, the method of manufacturing a semiconductor device according to Embodiment 1-2 includes the steps of: preparing the above-described wafer-bonding film with a dicing sheet; and thermosetting a wafer-bonding film of the wafer-bonding film with the dicing sheet and a semiconductor a bonding step of bonding the back surface of the wafer; cutting the semiconductor wafer together with the thermosetting wafer bonding film to form a wafer-shaped semiconductor wafer; and bonding the semiconductor wafer to the thermosetting wafer a picking step of the film together from the wafer-bonding film attached to the dicing sheet; and a wafer bonding step of bonding the semiconductor wafer to the adherend via the aforementioned thermosetting wafer bonding film.

In the method of manufacturing a semiconductor device according to Embodiment 1-2, a wafer bonding film with a dicing sheet is used, and in the method of manufacturing a semiconductor device according to Embodiment 1-1, a wafer bonding film is used as a single body. But other aspects are common. In the method of manufacturing a semiconductor device according to the embodiment 1-1, when the wafer bonding film is prepared and then bonded to the dicing sheet, the method of manufacturing the semiconductor device of the second embodiment can be used. Therefore, a method of manufacturing the semiconductor device of the embodiment 1-2 will be described below.

First, the wafer bonding film 10, 12 with the dicing sheet is prepared. Prepare the steps). The wafer bonding films 10, 12 with the dicing sheets can be suitably peeled off from the arbitrarily disposed separators on the wafer bonding films 3, 3' and used as follows. Hereinafter, a case where the wafer bonding film 10 with a dicing sheet is used will be described as an example with reference to FIGS. 1 to 3.

First, the semiconductor wafer 4 is crimped onto the semiconductor wafer attaching portion 3a of the wafer bonding film 3 in the wafer bonding film 10 with the dicing sheet, and is kept adhered and fixed (bonding step). This step is performed by pressing with a pressing means such as a pressure roller. The attachment temperature at the time of fixation is not particularly limited, and is, for example, preferably in the range of 40 to 90 °C.

Next, the semiconductor wafer 4 is cut (cutting step). Thereby, the semiconductor wafer 4 is cut into a predetermined size and singulated to manufacture the semiconductor wafer 5. The method of cutting is not particularly limited, and for example, it can be carried out from the circuit surface side of the semiconductor wafer 4 in accordance with a conventional method. In addition, in this step, for example, a cutting method or the like which is called a full cut until the wafer bonding film 10 of the dicing sheet is attached can be performed. The cutting device used in this step is not particularly limited, and a conventionally known device can be used. Further, since the semiconductor wafer 4 is bonded and fixed by the wafer bonding film 10 to which the dicing sheet is attached, wafer defects and wafer scattering can be suppressed, and damage of the semiconductor wafer 4 can be suppressed.

Next, in order to peel off the semiconductor wafer 5 bonded and fixed to the wafer bonding film 10 with the dicing sheet, picking up of the semiconductor wafer 5 is performed (pickup step). The method of picking up is not particularly limited, and various conventionally known methods can be employed. For example, each semiconductor wafer 5 is lifted up from the side of the wafer bonding film 10 with the dicing sheet, and picked up by a pick-up device. A method of taking the lifted semiconductor wafer 5 or the like.

The picking condition is preferably from 5 to 100 mm/sec, more preferably from 5 to 10 mm/sec, from the viewpoint of preventing fragmentation.

Here, when the adhesive layer 2 is an ultraviolet curing type, picking up is performed after irradiating the adhesive layer 2 with ultraviolet rays. Thereby, the adhesive force of the adhesive layer 2 to the wafer bonding film 3 is lowered, and the peeling of the semiconductor wafer 5 becomes easy. As a result, pickup can be performed without damaging the semiconductor wafer 5. The conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be appropriately set as necessary. Further, as a light source for ultraviolet irradiation, a known light source can be used. When the adhesive layer 2 is irradiated with ultraviolet rays in advance and cured, and the cured adhesive layer 2 is bonded to the wafer bonding film, ultraviolet irradiation is not required here.

Next, the picked semiconductor wafer 5 is bonded and fixed to the adherend 6 via the die bond film 3 (wafer bonding step). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, or a separately fabricated semiconductor wafer. The adherend 6 may be, for example, a deformed adherend that is easily deformed, or a non-deformable adherend (semiconductor wafer or the like) that is difficult to deform.

A conventionally known substrate can be used for the substrate. In addition, as the lead frame, a metal lead frame such as a Cu lead frame or a 42 alloy lead frame or a glass epoxy resin, BT (Bismaleimide-triazine), polyimine, or the like can be used. Made of an organic substrate. However, the substrate is not limited thereto, and includes a circuit board that can be used to fix and electrically connect the semiconductor wafer to the semiconductor wafer.

Next, since the wafer bonding film 3 is a thermosetting type, the semiconductor wafer 5 is bonded and fixed to the adherend 6 by heat curing, and the heat resistance is improved (thermal curing step). It can be carried out at a heating temperature of 80 to 200 ° C, preferably 100 to 175 ° C, more preferably 100 to 140 ° C. Further, the heating time may be 0.1 to 24 hours, preferably 0.1 to 3 hours, more preferably 0.2 to 1 hour. In addition, heat curing can be carried out under pressurized conditions. The pressurization condition is preferably in the range of 1 to 20 kg/cm ² , more preferably in the range of 3 to 15 kg/cm ² . The heat curing under pressure can be carried out, for example, in a chamber filled with an inert gas. The product obtained by bonding and fixing the semiconductor wafer 5 to the substrate or the like via the wafer bonding film 3 can be supplied to the reflow step.

The shear adhesive strength of the wafer bonded film 3 after heat curing is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa with respect to the adherend 6 . When the shear bonding strength of the wafer bonding film 3 is at least 0.2 MPa or more, the wafer bonding film 3 and the semiconductor wafer 5 or the adherend 6 are not caused by ultrasonic vibration or heating in this step during the wire bonding step. The bonding surface produces shear deformation. That is, the semiconductor wafer 5 does not move due to ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of wire bonding from being lowered.

Next, as shown in FIG. 3, the tip end of the terminal portion (internal lead) of the adherend 6 and the electrode pad (not shown) on the semiconductor wafer 5 are electrically connected by the bonding lead 7 as needed. (Wire bonding step). As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding can be carried out in the range of 80 to 250 ° C, preferably 80 to 220 ° C. In addition, It is carried out in a heating time of several seconds to several minutes. The wire connection can be performed by using the ultrasonic-based vibration energy and the pressure-based pressure-bonding energy in combination in a state where the heating is within the aforementioned temperature range. This step can be carried out without performing thermal curing of the wafer bonding film 3.

Next, as needed, as shown in FIG. 3, the semiconductor wafer 5 is packaged by the encapsulating resin 8 (packaging step). This step is performed to protect the semiconductor wafer 5 mounted on the adherend 6 and the bonding leads 7. This step can be carried out by molding a resin for encapsulation using a mold. As the encapsulating resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin encapsulation is usually carried out at 175 ° C for 60 to 90 seconds, but the heating conditions are not limited thereto, and for example, it may be cured at 165 to 185 ° C for several minutes. Thereby, the encapsulating resin 8 is cured and the semiconductor wafer 5 and the adherend 6 are fixed via the wafer bonding film 3. In other words, even when the post-cure step to be described later is not performed, the wafer bonding film 3 can be fixed in this step, which can contribute to reducing the number of manufacturing steps and shortening the manufacturing cycle of the semiconductor device. In the present packaging step, a method of embedding the semiconductor wafer 5 in a sheet-like package sheet may be employed (for example, refer to Japanese Laid-Open Patent Publication No. 2013-7028).

Next, heating is performed as needed to completely cure the encapsulating resin 8 which is not sufficiently cured in the above-described encapsulation step (post-cure step). Even in the case where the wafer bonding film 3 is not completely thermally cured in the encapsulating step, the wafer bonding film 3 can be completely thermally cured together with the encapsulating resin 8 in this step. The heating temperature in this step varies depending on the type of the encapsulating resin, and is, for example, in the range of 165 to 185 ° C, and the heating time is about 0.5 to 8 hours.

The semiconductor wafer 5 may be packaged with the encapsulating resin 8 and the encapsulating resin 8 may be cured by performing wire bonding without pre-fixing by the wafer bonding step, without performing a thermal curing step based on the heat treatment of the wafer bonding film 3. (post cure). At this time, the shear adhesive strength at the time of pre-fixing of the wafer bonding film 3 is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa with respect to the adherend 6 . When the shear bonding strength at the time of pre-fixing of the die-bonding film 3 is at least 0.2 MPa or more, the wire bonding film is not subjected to ultrasonic vibration or heating in this step even if the wire bonding step is not performed through the heating step. 3 shear deformation occurs with the bonding surface of the semiconductor wafer 5 or the adherend 6. That is, the semiconductor wafer is not moved by the ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of the wire bonding from being lowered. The pre-fixing state is a state in which the wafer bonding film 3 is cured to such an extent that the curing reaction of the thermosetting wafer bonding film 3 is not completed (in a semi-cured state), so as not to affect the subsequent steps. The state in which the semiconductor wafer 5 is fixed. In the case of performing the wire bonding without the heat curing step by the heat treatment based on the wafer bonding film 3, the above-described post-curing step corresponds to the heat curing step in the present specification.

<<Second invention>>

The second invention will be described here.

Problem to be solved by the second invention

In order to exhibit high thermal conductivity of the wafer bonding film, a method of filling a large amount of thermally conductive particles can be considered. However, when the thermally conductive particles show a single peak in the particle size distribution, a close packed structure cannot be formed, and it is difficult to fill a large amount.

On the other hand, in the state in which the thermally conductive particles are filled in the wafer bonding film, the viscosity of the wafer bonding film is increased due to the interaction between the thermally conductive particles and the resin, so that the fluidity is lowered, and the wafer bonding film may not sufficiently follow. Concavities and convexities of a substrate such as a printed circuit board. When the unevenness followability of the wafer bonding film is poor, a gap is formed between the wafer bonding film and the substrate. The voids reduce the heat dissipation of the semiconductor device. Further, in the reflow step, the wafer bonding film is easily peeled off from the adherend due to the void.

The second aspect of the present invention has been made in view of the above problems, and an object of the invention is to provide a thermosetting wafer-bonding film capable of filling a large amount of thermally conductive particles and having excellent unevenness and wettability, and using thermosetting. A wafer-bonding film with a dicing sheet of a die bond film and a method of manufacturing a semiconductor device.

The second aspect of the invention relates to a thermosetting wafer-bonding film comprising thermally conductive particles, wherein in the particle size distribution of the thermally conductive particles, a peak A is present in a particle size range of less than 2 μm, and a particle diameter of 2 μm or more is present. There is a peak B in the range, and the ratio of the particle diameter of the peak B to the particle diameter of the peak A is 5 to 20, and the thermal conductivity of the thermosetting wafer bonding film after heat curing is 1 W/m. K or more.

In the second aspect of the invention, since the thermally conductive particles forming the peak A can be filled between the thermally conductive particles forming the peak B (in the gap), the thermally conductive particles can be filled in a large amount. Further, since the ratio of the particle diameter of the peak B to the particle diameter of the peak A is within a specific range, good unevenness followability and wet reflow resistance can be obtained.

The thermal conductivity of the above thermally conductive particles is preferably 12 W/m. K or more. Thereby, excellent thermal conductivity can be obtained.

In the particle size distribution of the thermally conductive particles, it is preferred that the peak A is present in a particle diameter range of 0.3 μm or more and less than 2 μm.

In the particle size distribution of the thermally conductive particles, it is preferred that the peak B be present in a particle diameter range of 2 μm to 20 μm.

The average particle diameter of the thermally conductive particles is preferably from 1 to 10 μm. Thereby, more favorable unevenness followability can be obtained.

The thickness of the above-mentioned thermosetting wafer bonding film is preferably 50 μm or less.

The sphericity of the thermally conductive particles is preferably 0.95 or more. Thereby, the contact area of the thermally conductive particles and the resin is small, and the fluidity at a normal wafer bonding temperature (120 ° C to 130 ° C) can be improved. Thereby, more favorable unevenness followability can be obtained.

The thermally conductive particles are preferably at least one selected from the group consisting of aluminum hydroxide particles, zinc oxide particles, aluminum nitride particles, tantalum nitride particles, niobium carbide particles, magnesium oxide particles, and boron nitride particles. These are easy to obtain particles having high thermal conductivity and high sphericity.

The second invention is also a method of manufacturing a semiconductor device, comprising the steps of: preparing the thermosetting wafer bonding film; and bonding the semiconductor wafer wafer to the adherend via the thermosetting wafer bonding film; step.

The second invention is also a wafer bonding film for a dicing sheet on which a thermosetting type wafer bonding film is laminated on a dicing sheet, and the dicing sheet is laminated with a binder layer on a substrate.

The second invention is also a method of manufacturing a semiconductor device, including a step of preparing the above-mentioned wafer bonding film with a dicing sheet; a step of bonding the thermosetting wafer bonding film of the dicing wafer-bonding film to the back surface of the semiconductor wafer; and the semiconductor wafer and a step of forming a wafer-shaped semiconductor wafer by cutting the thermosetting wafer bonding film together; a step of picking up the semiconductor wafer together with the thermosetting wafer bonding film from the wafer bonding film with the dicing sheet; and passing the heat A step of bonding a semiconductor wafer to the adherend by a solid wafer bonding film.

Hereinafter, the second invention will be described in detail with reference to the second embodiment, but the second invention is not limited thereto.

[Embodiment 2] (wafer bonding film with cut sheet)

The thermosetting wafer bonding film (hereinafter also referred to as "wafer bonding film") of the second embodiment and the wafer bonding film with the dicing sheet are described below. In the wafer bonding film of the second embodiment, a wafer bonding film in a state in which the dicing sheet is not bonded to the wafer bonding film with a dicing sheet described below is exemplified. Therefore, the wafer bonding film with the dicing sheet will be described below, and the wafer bonding film will be described.

As shown in FIG. 4, the wafer bonding film 210 with a dicing sheet has a structure in which a thermosetting wafer bonding film 203 is laminated on the dicing sheet 11. The dicing sheet 11 is formed by laminating a binder layer 2 on a substrate 1, and a wafer bonding film 203 is provided on the binder layer 2. The wafer bonding film 203 is provided with a workpiece attaching portion 203a for attaching a workpiece and is disposed in the work. The peripheral portion 203b around the periphery of the attachment portion 203a. As shown in Fig. 5, the modification may be a wafer bonding film 212 provided with a dicing sheet of the wafer bonding film 203' only at the workpiece attaching portion.

The thermal conductivity of the wafer bonding films 203, 203' after heat curing is 1 W/m. K or more, preferably 1.2 W/m. K or more, more preferably 1.5W/m. K or more. The thermal conductivity after heat curing is 1W/m. Since K is more than the above, the semiconductor device manufactured using the wafer bonding films 203 and 203' is excellent in heat dissipation. The higher the thermal conductivity of the wafer bonding films 203, 203' after heat curing, the better, but for example, 20 W/m. Below K.

The "thermal conductivity after heat curing" means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

The wafer bonding films 203, 203' contain thermally conductive particles.

The thermal conductivity of the thermally conductive particles is preferably 12 W/m. K or more. The upper limit of the thermal conductivity of the thermally conductive particles is not particularly limited, and is, for example, 400 W/m. Below K.

The thermal conductivity of the thermally conductive particles can be estimated from the crystal structure of the thermally conductive particles obtained by X-ray structural analysis.

In the particle size distribution of the thermally conductive particles, there are two or more peaks. Specifically, a peak A exists in a particle size range of less than 2 μm, and a peak B exists in a particle diameter range of 2 μm or more. In the wafer bonding films 203 and 203', thermally conductive particles forming the peak A are filled between the thermally conductive particles forming the peak B. Thereby, a large amount of thermal conductive particles can be filled.

In the particle size distribution of the thermally conductive particles, since the peak A exists in a particle diameter range of less than 2 μm, the thermally conductive particles can be filled in a large amount. Peak A It is preferably present in a particle size range of 1 μm or less.

The peak A is preferably present in a particle size range of 0.3 μm or more, more preferably in a particle diameter range of 0.5 μm or more. When it is 0.3 μm or more, good unevenness followability can be obtained.

In the particle size distribution of the thermally conductive particles, since the peak B exists in the particle diameter range of 2 μm or more, the thermally conductive particles can be filled in a large amount. Good bump followability is obtained. The peak B is preferably present in a particle size range of 4 μm or more.

The peak B is preferably present in a particle size range of 20 μm or less, and more preferably in a particle diameter range of 12 μm or less. When the thickness is 20 μm or less, the wafer bonding films 203 and 203' can be made thinner, and the heat from the wafer can be efficiently dissipated to the adherend by the thinning.

In the particle size distribution of the thermally conductive particles, there may be peaks other than the peak A and the peak B.

The particle size distribution of the thermally conductive particles can be measured by the method described in the examples.

The ratio of the particle diameter of the peak B to the particle diameter of the peak A (the particle diameter of the peak B / the particle diameter of the peak A) is 5 or more, preferably 7 or more. Since it is 5 or more, a large amount of thermal conductive particles can be filled, and favorable unevenness followability can be obtained. The ratio of the particle diameter of the peak B to the particle diameter of the peak A is 20 or less, preferably 18 or less, more preferably 15 or less. Since it is 20 or less, good wet-resistance reflowability can be obtained.

In the particle size distribution of the thermally conductive particles, when two or more peaks are present, two or more types of thermally conductive particles having different average particle diameters may be blended.

The average particle diameter of the thermally conductive particles is preferably 1 μm or more, and more preferably 1.5 μm or more. Since it is 1 μm or more, good unevenness followability can be obtained. Further, the average particle diameter of the thermally conductive particles is preferably 10 μm or less, more preferably 8 μm or less. Since it is 10 μm or less, good film moldability can be obtained.

The average particle diameter of the thermally conductive particles can be measured by the method described in the examples.

The specific surface area of the thermally conductive particles is preferably 0.5 m ² /g or more, more preferably 0.7 m ² /g or more. When it is 0.5 m ² /g or more, the elastic modulus after curing becomes high and the reflow resistance is excellent. Further, the specific surface area of the thermally conductive particles is preferably 8 m ² /g or less, more preferably 6.5 m ² /g or less. When it is 8 m ² /g or less, good unevenness followability can be obtained.

The specific surface area of the thermally conductive particles can be measured by the method described in the examples.

The shape of the thermally conductive particles is not particularly limited, and for example, a sheet, a needle, a filament, a sphere, or a scaly particle may be used, and a particle having a sphericity of 0.9 or more is preferable, and more preferably 0.95 or more. Thereby, the contact area of the thermally conductive particles and the resin can be made small, and the fluidity at 120 ° C to 130 ° C can be improved. The closer the sphericity is to 1, the closer it is to the true sphere.

The sphericity of the thermally conductive particles can be measured by the following method.

Determination of sphericity

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. SEM (Electronic Scanning Microscopy) Mirror) A photograph was taken of the obtained ash, and the sphericity was calculated from the area and the circumference of the observed particles by the following formula. The sphericity was measured for 100 particles using an image processing apparatus (Sysmex Corporation: FPIA-3000).

(sphericity) = {4π × (area) ÷ (circumference) ² }

From the viewpoint of easily obtaining particles having high thermal conductivity and high sphericity, the thermally conductive particles are preferably alumina particles (thermal conductivity: 36 W/m.K), zinc oxide particles (thermal conductivity: 54 W/m. K), Aluminum nitride particles (thermal conductivity: 150 W/m.K), tantalum nitride particles (thermal conductivity: 27 W/m.K), niobium carbide particles (thermal conductivity: 200 W/m.K), magnesium oxide particles (thermal conductivity) : 59 W / m. K), boron nitride particles (thermal conductivity: 60 W / m. K) and the like. In particular, the alumina particles have a high thermal conductivity, and are preferable from the viewpoint of dispersibility and ease of availability. Further, since the boron nitride particles have a higher thermal conductivity, they can be suitably used.

The thermally conductive particles are preferably treated with a decane coupling agent (pretreatment). Thereby, the dispersibility of the thermal conductive particles becomes good, and the thermal conductive particles can be filled in a large amount.

A suitable decane coupling agent is as described in the first embodiment.

The method of treating the thermally conductive particles by a decane coupling agent is not particularly limited, and examples thereof include a wet method in which a thermally conductive particle and a decane coupling agent are mixed in a solvent, and a thermally conductive particle and a decane couple in a gas phase. A dry method in which the crosslinking agent is treated.

The treatment amount of the decane coupling agent is not particularly limited, and it is preferred to treat 0.05 to 5 parts by weight of the decane coupling agent with respect to 100 parts by weight of the thermally conductive particles.

The content of the thermally conductive particles is preferably 75% by weight or more, more preferably 80% by weight or more, and still more preferably 85% by weight or more based on the entire wafer bonding films 203 and 203'. When the amount is 75 wt% or more, the semiconductor device manufactured using the wafer bonding films 203 and 203' is excellent in heat dissipation. In addition, the content of the thermally conductive particles is preferably as large as possible, but is, for example, 93% by weight or less from the viewpoint of film formability.

The wafer bonding films 203 and 203' preferably contain a resin component such as a thermosetting resin or a thermoplastic resin.

Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. Particularly preferred is an epoxy resin containing less ionic impurities such as etching semiconductor wafers. Further, the curing agent for the epoxy resin is preferably a phenol resin.

The epoxy resin is not particularly limited as long as it is a binder used for wafer bonding, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenation double can be used. Phenol type A, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolak type, o-cresol novolak type, trihydroxyphenylmethane type, tetrakis(phenylhydroxy)ethane (Tetraphenylolethane) type Such as a difunctional epoxy resin, a polyfunctional epoxy resin; or an epoxy resin such as an intramethylene uregar type, a triglycidyl isocyanurate type or a glycidylamine type. They may be used singly or in combination of two or more. Among these epoxy resins, particularly preferred are novolak type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetrakis (phenyl). Hydroxy) ethane type epoxy resin. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, an epoxy resin which is liquid at room temperature is preferred.

In this specification, liquid means that the viscosity at 25 ° C is less than 5000 Pa. s. The viscosity can be measured using the model HAAKE Roto VISCO1 manufactured by Thermo Fisher Scientific K.K.

The softening point of the epoxy resin is preferably 100 ° C or less from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The softening point of the epoxy resin can be measured by the ring and ball method prescribed in JIS K7234-1986.

Further, the phenol resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butylphenol novolak resin, and a nonylphenol novolak resin. Such as a novolac type phenolic resin; a resol type phenolic resin, polyoxystyrene such as polyoxystyrene. These may be used alone or in combination of two or more. Among these phenol resins, a phenol novolac resin and a phenol aralkyl resin are preferred. This is because the connection reliability of the semiconductor device can be improved.

The softening point of the phenol resin is preferably 100 ° C or lower, more preferably 80 ° C or lower from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The softening point of the phenol resin can be measured by the ring and ball method prescribed in JIS K 6910-2007.

The ratio of the epoxy resin to the phenolic resin is, for example, preferably phenolic. The hydroxyl group in the resin is blended in an amount of from 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitable for 0.8~1.2 equivalents. In other words, when the blending ratio of the two is out of the above range, a sufficient curing reaction is not performed, and the properties of the cured epoxy resin are likely to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutadiene. Resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon, 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET, PBT, polyamidoguanidine Imine resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is less ionic impurities, has high heat resistance, and can secure the reliability of a semiconductor wafer is particularly preferable.

A suitable acrylic resin is as described in the first embodiment.

The content of the resin component is preferably 7% by weight or more based on the entire wafer bonding films 203 and 203'. The content of the resin component is preferably 25% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less based on the entire wafer bonding films 203 and 203'.

The blending ratio of the thermosetting resin in the resin component (the total amount of the thermosetting resin and the thermoplastic resin) is not particularly limited as long as the wafer bonding films 203 and 203' exhibit a function as a thermosetting type when heated under predetermined conditions. From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, it is preferably in the range of 75 to 99% by weight, more preferably in the range of 85 to 98% by weight.

The blending ratio of the thermoplastic resin in the resin component is preferably in the range of 1 to 25% by weight, more preferably 2 to 15% by weight, from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The wafer bonding films 203, 203' preferably comprise a curing catalyst. Thereby, thermal curing of the epoxy resin and a curing agent such as a phenol resin can be promoted. The curing catalyst is not particularly limited, and examples thereof include tetraphenylboron tetraphenylphosphonium (trade name: TPP-K), tetrakis(p-tolylboron)tetraphenylphosphonium (trade name: TPP-MK), and triphenylene. Phosphorus-boron-based curing catalysts such as phosphine triphenylborane (trade name: TPP-S) (all manufactured by Beixing Chemical Industry Co., Ltd.). Among them, tetrakis(p-tolylboron)tetraphenylphosphonium is preferred from the viewpoint of excellent latent property and good storage stability at room temperature.

The content of the curing catalyst can be appropriately set, and is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermosetting resin.

When the wafer bonding films 203 and 203' are crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer is added as a crosslinking agent at the time of production. Just fine. Thereby, the adhesive property at a high temperature can be improved, and the heat resistance can be improved.

A suitable crosslinking agent is as described in the first embodiment.

Further, in the wafer bonding films 203 and 203', a filler other than the thermally conductive particles can be appropriately prepared depending on the application. The formulation of the filler can adjust the modulus of elasticity and the like. The specifics of the filler are, for example, the description in the first embodiment.

In the wafer bonding film 203, 203', in addition to the filler, Other additives are appropriately formulated as needed. Specific examples of the other additives are as described in the first embodiment.

The laminated structure of the die-bonding films 203 and 203' is not particularly limited, and examples thereof include a structure in which only a single layer of the adhesive layer is formed, and a multilayer structure in which an adhesive layer is formed on one or both sides of the core material. . The core material may, for example, be a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a glass fiber. A resin substrate, a ruthenium substrate, or a glass substrate reinforced with a plastic non-woven fabric.

The thickness of the wafer bonding films 203 and 203' (the total thickness in the case of the laminate) is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. Further, the thickness of the die-bonding films 203 and 203' is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less.

With respect to the substrate 1, the adhesive layer 2, and the die-bonding films 203 and 203', it is possible to prevent static electricity from being generated during adhesion and peeling, thereby causing the semiconductor wafer or the like to be charged and causing the circuit to be broken. The wafer-bonding films 210 and 212 with the dicing sheet described above have an antistatic function. The antistatic function can be carried out by adding an antistatic agent or a conductive material to the substrate 1, the adhesive layer 2, the die bond films 203 and 203', and attaching the substrate 1 to the substrate 1. A conductive layer made of a charge transfer complex, a metal film, or the like. Among these forms, it is preferred that the impurity ions which may deteriorate the semiconductor wafer are less likely to be generated. Conductive material formulated for the purpose of imparting conductivity, improving conductivity, etc. Examples of the material include spherical, needle-shaped, sheet-like metal powder such as silver, aluminum, gold, copper, nickel, and a conductive alloy, amorphous carbon black, and graphite.

The wafer bonding films 203, 203' of the wafer-bonding films 210, 212 with the dicing sheets are preferably protected by a separator (not shown). The separator has a function of providing a protective material for protecting the wafer bonding films 203, 203'. Further, the separator can be further used as a support substrate when the wafer bonding films 203 and 203' are transferred to the adhesive layer 2. The separator is peeled off when the workpiece is bonded to the wafer bonding films 203, 203' of the wafer bonding films 210, 212 to which the dicing sheets are attached. As the separator, a plastic film surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, or a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. , paper, etc.

The wafer bonding films 210 and 212 with the dicing sheets can be manufactured by the method described in the first embodiment or the like.

In the second embodiment, the semiconductor device can be manufactured by the same method as in the first embodiment.

<<The third invention>>

The third invention will be described here.

The problem to be solved by the third invention

In a semiconductor device, a high-frequency device (RF device) generates a large amount of heat, and heat dissipation is important.

On the other hand, sometimes Moisture Sensitivity Levels (MSL, moisture sensitive) are required for semiconductor devices such as high-frequency devices that satisfy the moisture absorption reflow test. Sensitivity level 1 reliability. However, the conventional wafer bonding film has low adhesion to the lead frame, and peeling may occur between the wafer bonding film and the lead frame, and there is room for improvement in reliability.

The third aspect of the present invention has been made in view of the above problems, and an object of the invention is to provide a thermosetting wafer bonding film which can obtain a semiconductor device having high heat dissipation and excellent reliability, and a dicing sheet using a thermosetting wafer bonding film. A wafer bonding film and a method of manufacturing a semiconductor device.

The inventors of the present invention have studied the thermosetting wafer bonding film in order to solve the above conventional problems. As a result, it has been found that a semiconductor device having high heat dissipation and excellent reliability can be obtained by the following technique, and thus the third invention has been completed.

The third aspect of the invention relates to a thermosetting wafer bonding film comprising thermally conductive particles, wherein the content of the thermally conductive particles is 75% by weight or more based on the total amount of the thermosetting wafer bonding film, and the thermosetting wafer bonding film is cured. The linear expansion coefficient of the obtained cured product at a glass transition temperature or lower is 5 ppm/K to 50 ppm/K, and the linear expansion coefficient at a temperature exceeding the glass transition temperature of the cured product is 150 ppm/K or less.

In the third aspect of the invention, by adjusting a large amount of thermally conductive particles, the coefficient of linear expansion below the glass transition temperature of the cured product is adjusted to 5 ppm/K to 50 ppm/K, and the temperature of the cured product exceeding the glass transition temperature is set. The lower linear expansion coefficient is adjusted to 150 ppm/K or less. In the thermosetting wafer bonding film of the third aspect of the invention, the linear expansion coefficient below the glass transition temperature and the linear expansion coefficient at a temperature exceeding the glass transition temperature are close to the linear expansion coefficient of the main component of the lead frame, that is, copper. 16.8ppm/K, so it is progressing In the reflow step of heating at a high temperature (for example, 260 ° C), generation of stress due to a difference in linear expansion can be suppressed, and a semiconductor device excellent in reliability can be obtained.

The thermosetting die-bonding film of the third invention preferably has a thermal conductivity of 12 W/m. K or more.

In the thermosetting wafer bonded film of the third aspect of the invention, it is preferable that the cured product has a storage modulus (E') at 260 ° C of 1 GPa or less.

The third invention is also a method of manufacturing a semiconductor device, comprising the steps of: preparing the thermosetting wafer bonding film; and bonding the semiconductor wafer to the adherend via the thermosetting wafer bonding film; step.

The third invention is also a wafer bonding film relating to a dicing sheet on which a thermosetting type wafer bonding film is laminated on a dicing sheet, the dicing sheet being laminated with a binder layer on a substrate.

The third invention is also a method of manufacturing a semiconductor device, comprising the steps of: preparing the wafer bonding film with the dicing sheet; and using the thermosetting wafer bonding film and the semiconductor crystal of the wafer bonding film with the dicing sheet a step of bonding the back surface of the circle; cutting the semiconductor wafer together with the thermosetting wafer bonding film to form a wafer-shaped semiconductor wafer; and using the semiconductor wafer together with the thermosetting wafer bonding film a step of picking up a wafer-bonding film with a dicing sheet; and a step of bonding the above-mentioned semiconductor wafer wafer to the adherend via the above-described thermosetting wafer bonding film.

Hereinafter, the third invention will be described in detail with reference to the third embodiment, but The three inventions are not limited thereto.

[Embodiment 3] (wafer bonding film with cut sheet)

The thermosetting wafer bonding film of the third embodiment (hereinafter also referred to as "wafer bonding film") and the wafer bonding film with the dicing sheet are described below. In the wafer bonding film of the third embodiment, a wafer bonding film in a state in which the dicing sheet is not bonded to the wafer bonding film with a dicing sheet described below is exemplified. Therefore, the wafer bonding film with the dicing sheet will be described below, and the wafer bonding film will be described.

As shown in FIG. 6, the wafer bonding film 310 with a dicing sheet has a structure in which a thermosetting wafer bonding film 303 is laminated on the dicing sheet 11. The dicing sheet 11 is formed by laminating a binder layer 2 on a substrate 1, and a wafer bonding film 303 is provided on the binder layer 2. The wafer bonding film 303 is provided with a workpiece attaching portion 303a for attaching a workpiece and a peripheral portion 303b disposed around the periphery of the workpiece attaching portion 303a. As shown in Fig. 7, the modification may be a wafer bonding film 312 provided with a dicing sheet of the wafer bonding film 303' only at the workpiece attaching portion.

The linear expansion coefficient of the cured product obtained by curing the wafer bonded films 303 and 303' is not more than 5 ppm/K. Since it is 5 ppm/K or more, it is possible to suppress the occurrence of stress caused by the difference in linear expansion between the wire bonding films 303 and 303' and the linear expansion of the adherend such as the lead frame in the reflowing step, and the reliability is excellent. Semiconductor device. The coefficient of linear expansion below the glass transition temperature of the cured product is preferably 10ppm/K or more. On the other hand, the linear expansion coefficient of the cured product at or below the glass transition temperature is 50 ppm/K or less. Since it is 50 ppm/K or less, it is possible to suppress the occurrence of stress caused by the difference between the linear expansion of the wafer bonding films 303 and 303' and the linear expansion of the adherend such as the lead frame in the reflow step, and the reliability is excellent. Semiconductor device. The coefficient of linear expansion below the glass transition temperature of the cured product is preferably 40 ppm/K or less.

The linear expansion coefficient at a temperature exceeding the glass transition temperature of the cured product obtained by curing the wafer bonding films 303 and 303' is 150 ppm/K or less. Since it is 150 ppm/K or less, it is possible to suppress the occurrence of stress caused by the difference in linear expansion between the wire bonding films 303 and 303' and the linear expansion of the adherend such as the lead frame in the reflowing step, and it is possible to obtain excellent reliability. Semiconductor device. The linear expansion coefficient at a temperature exceeding the glass transition temperature of the cured product is preferably 140 ppm/K or less, more preferably 120 ppm/K or less.

On the other hand, the lower limit of the coefficient of linear expansion at a temperature exceeding the glass transition temperature of the cured product is not particularly limited, and is, for example, 5 ppm/K or more. When the concentration is 5 ppm/K or more, it is possible to suppress the occurrence of stress caused by the difference in linear expansion between the linear expansion of the wafer bonding films 303 and 303' and the adherend such as the lead frame in the reflow process, and to obtain a semiconductor excellent in reliability. Device.

The "cured material" is a cured product obtained by heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours. The coefficient of linear expansion can be measured by the method described in the examples.

The coefficient of linear expansion of the cured product can be controlled by the content of the thermally conductive particles or the like. For example, by increasing the content of thermally conductive particles, the linear expansion can be reduced. Expansion coefficient.

The glass transition temperature of the cured product obtained by curing the wafer bonding films 303 and 303' is preferably 80 °C or higher. When the temperature is 80 ° C or higher, it is possible to suppress abrupt physical property changes in the normal use temperature range of the semiconductor device and the temperature range of the thermal cyclotron reliability test. On the other hand, the glass transition temperature of the cured product is not particularly limited, and is, for example, 200 ° C or lower, preferably 120 ° C or lower.

The glass transition temperature of the cured product can be measured by the method described in the examples.

The glass transition temperature of the cured product can be controlled by a crosslinking density or the like of a functional group based on a thermosetting resin (for example, an epoxy resin, a phenol resin). The glass transition temperature can be increased, for example, by using a thermosetting resin having a large number of functional groups in the molecule.

The storage modulus (E') at 260 ° C of the cured product obtained by curing the wafer bonded films 303 and 303' is preferably 1 GPa or less. When the thickness is 1 GPa or less, the stress relaxation property is excellent, and internal stress generated in the semiconductor device during heat change can be alleviated, and peeling from the adherend is less likely to occur. The storage modulus at 260 ° C of the cured product is preferably 1 MPa or more. When it is 1 MPa or more, it is less likely to cause cohesive failure at a high temperature and excellent reflow resistance.

The storage modulus of the cured product can be measured by the method described in the examples.

The melt adhesion at 130 ° C of the wafer bonding film 303, 303' is preferably 300 Pa. Below s, more preferably 280Pa. s below, and more preferably 250Pa. s below. 300Pa. Below s, at the usual wafer bonding temperature (120 ° C The fluidity at ~130 ° C) is high, and it is possible to follow the irregularities of the adherend such as a printed circuit board, and to suppress the occurrence of voids. In addition, the melt viscosity at 130 ° C is preferably 10 Pa. Above s, more preferably 20Pa. More than s, and more preferably 50Pa. s above. 10Pa. When s or more, the shape of the film can be maintained.

The melt viscosity at 130 ° C is a value obtained by setting the shear rate as a measurement condition to 5 sec ^-1 .

The melt viscosity at 130 ° C of the wafer bonding films 303 and 303' can be controlled by the average particle diameter of the thermally conductive particles, the softening point of the epoxy resin, the softening point of the phenol resin, and the like. For example, by setting the average particle diameter of the thermally conductive particles to be large, lowering the softening point of the epoxy resin, and lowering the softening point of the phenol resin, the melt viscosity at 130 ° C can be lowered.

The thermal conductivity of the wafer bonding films 303, 303' after heat curing is preferably 1 W/m. K or more, more preferably 1.2 W/m. Above K, and more preferably 1.5W//m. K or more. The thermal conductivity after heat curing is 1W/m. Since K is more than the above, the semiconductor device manufactured using the wafer bonding films 303 and 303' is excellent in heat dissipation. The higher the thermal conductivity of the wafer bonding films 303, 303' after heat curing, the better, for example, 20 W/m. Below K.

The "thermal conductivity after heat curing" means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

The wafer bonding films 303, 303' contain thermally conductive particles.

The thermal conductivity of the thermally conductive particles is preferably 12 W/m. K or more, more preferably 20W/m. K or more. The upper limit of the thermal conductivity of the thermally conductive particles is not particularly limited, and is, for example, 400 W/m. Below K, preferably 50 W/m. Below K.

The thermal conductivity of the thermally conductive particles can be estimated from the crystal structure of the thermally conductive particles obtained by X-ray structural analysis.

The average particle diameter of the thermally conductive particles is 3 μm or more, and preferably 3.5 μm or more. Since it is 3 μm or more, the fluidity at 120 ° C to 130 ° C can be improved. Further, the thermal conductive particles have an average particle diameter of 7 μm or less, preferably 6 μm or less. Since it is 7 μm or less, good film moldability can be obtained.

The average particle diameter of the thermally conductive particles can be measured by the method described in the examples.

In the particle size distribution of the thermally conductive particles, it is preferred to have two or more peaks. Specifically, it is preferred that a first peak exists in a particle diameter range of 0.2 to 0.8 μm, and a second peak exists in a particle diameter range of 3 to 15 μm. Thereby, the thermally conductive particles forming the first peak can be filled between the thermally conductive particles forming the second peak (in the gap), so that the thermally conductive particles can be filled in a large amount.

When the particle diameter of the first peak is less than 0.2 μm, the viscosity of the wafer bonding films 303 and 303' tends to be high, and the unevenness of the adherend tends not to follow. When the particle diameter of the first peak exceeds 0.8 μm, a large amount of filling of the thermally conductive particles tends to be difficult.

Further, when the particle diameter of the second peak is less than 3 μm, it tends to be difficult to form a large amount of the thermally conductive particles. Further, the viscosity of the wafer bonding films 303 and 303' tends to be too high to follow the unevenness of the adherend. When the particle diameter of the second peak exceeds 15 μm, it becomes difficult to form a thin film of the die-bonding films 303 and 303'.

In the particle size distribution of the thermally conductive particles, there are two or more peaks to be present In this case, two or more types of thermally conductive particles having different average particle diameters may be blended.

The shape of the thermally conductive particles is not particularly limited, and for example, a sheet, a needle, a filament, a sphere, or a scaly particle may be used, and a particle having a sphericity of 0.9 or more is preferable, and more preferably 0.95 or more. Thereby, the contact area of the thermally conductive particles and the resin can be made small, and the fluidity at 120 ° C to 130 ° C can be improved. The closer the sphericity is to 1, the closer it is to the true sphere.

The sphericity of the thermally conductive particles can be measured by the following method.

Determination of sphericity

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. A photograph was taken of the obtained ash by SEM, and the sphericity was calculated from the area and the circumference of the observed particles by the following formula. The sphericity was measured for 100 particles using an image processing apparatus (Sysmex Corporation: FPIA-3000).

(sphericity) = {4π × (area) ÷ (circumference) ² }

From the viewpoint of easily obtaining particles having high thermal conductivity and high sphericity, the thermally conductive particles are preferably alumina particles (thermal conductivity: 36 W/m.K), zinc oxide particles (thermal conductivity: 54 W/m. K), Aluminum nitride particles (thermal conductivity: 150 W/m.K), tantalum nitride particles (thermal conductivity: 27 W/m.K), niobium carbide particles (thermal conductivity: 200 W/m.K), magnesium oxide particles (thermal conductivity) : 59 W / m. K), boron nitride particles (thermal conductivity: 60 W / m. K) and the like. In particular, the alumina particles have a high thermal conductivity and are preferred from the viewpoint of dispersibility and ease of availability. Further, since the boron nitride particles have a higher thermal conductivity, they can be suitably used.

The thermally conductive particles are preferably treated with a decane coupling agent (pretreatment). Thereby, the dispersibility of the thermal conductive particles is improved, and the thermally conductive particles can be sufficiently filled.

A suitable decane coupling agent is as described in the first embodiment.

The method of treating the thermally conductive particles by a decane coupling agent is not particularly limited, and examples thereof include a wet method in which a thermally conductive particle and a decane coupling agent are mixed in a solvent, and a coupling of a thermally conductive particle and a decane in a gas phase. Dry method for treating the agent.

The treatment amount of the decane coupling agent is not particularly limited, and it is preferred to treat 0.05 to 5 parts by weight of the decane coupling agent with respect to 100 parts by weight of the thermally conductive particles.

The content of the thermally conductive particles is 75% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more based on the entire wafer bonding films 303 and 303'. Since it is 75% by weight or more, the semiconductor device manufactured using the wafer bonding films 303 and 303' is excellent in heat dissipation. The coefficient of linear expansion below the glass transition temperature of the cured product can be easily adjusted to 5 ppm/K to 30 ppm/K, and the coefficient of linear expansion at a temperature exceeding the glass transition temperature of the cured product can be easily adjusted to 100 ppm/ Below K. In addition, the content of the thermally conductive particles is preferably as large as possible, but is, for example, 93% by weight or less from the viewpoint of film formability.

The wafer bonding films 303 and 303' preferably contain a resin component such as a thermosetting resin or a thermoplastic resin.

The thermosetting resin may, for example, be a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin or a heat. A solid polyimine resin or the like. These resins may be used singly or in combination of two or more. It is particularly preferable to etch an epoxy resin having a small content of ionic impurities or the like in a semiconductor wafer. Further, the curing agent for the epoxy resin is preferably a phenol resin.

The epoxy resin is not particularly limited as long as it is generally used as an adhesive for wafer bonding, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol can be used. A type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, trihydroxyphenylmethane type, tetrakis(phenylhydroxy)ethane type and the like An epoxy resin, a polyfunctional epoxy resin; or an epoxy resin such as a carbendazim type, a triglycidyl isocyanurate type or a glycidylamine type. They may be used singly or in combination of two or more. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetrakis(phenylhydroxy)ethane type epoxy resin is particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

Further, from the viewpoint of being soft at normal temperature and imparting flexibility to the die-bonding films 303 and 303', a bisphenol A epoxy resin is preferred. From the viewpoint of being excellent in high heat resistance and chemical resistance, being soft at room temperature, and imparting flexibility to the die-bonding films 303 and 303', a bisphenol F-type epoxy resin is preferable.

From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, an epoxy resin which is liquid at room temperature is preferred.

In this specification, liquid means that the viscosity at 25 ° C is less than 5000. Pa. s. The viscosity can be measured using the model HAAKE Roto VISCO1 manufactured by Thermo Fisher Scientific K.K.

From the viewpoint of improving the fluidity at 120 ° C to 130 ° C, the softening point of the epoxy resin is preferably 100 ° C or lower, more preferably 80 ° C or lower. More preferably, it is 70 ° C or less.

The softening point of the epoxy resin can be measured by the ring and ball method prescribed in JIS K 7234-1986.

When the wafer bonding films 303 and 303' contain an epoxy resin which is liquid at room temperature, it is preferable to further contain an epoxy resin having a softening point of 40 ° C to 100 ° C. Thereby, the wafer bonding films 303 and 303' which are excellent in handleability while suppressing adhesion at room temperature can be obtained.

When the wafer bonding film 303, 303' contains an epoxy resin which is liquid at room temperature and an epoxy resin having a softening point of 40 ° C to 100 ° C, the content of the epoxy resin which is liquid at room temperature is 100 weight of the epoxy resin. The % is preferably 10% by weight or more, more preferably 20% by weight or more. Further, the content of the epoxy resin which is liquid at room temperature is preferably 80% by weight or less, more preferably 70% by weight or less, based on 100% by weight of the epoxy resin.

Further, the phenol resin acts as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butylphenol novolak resin, and a nonylphenol novolac resin. A novolak type phenol resin such as a resin; a polyoxystyrene such as a resol type phenol resin or polyoxy oxy styrene; and the like. These may be used alone or in combination of two or more. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferred. This is because it can improve the semiconductor Connection reliability of the device.

The softening point of the phenol resin is preferably 100 ° C or lower, more preferably 80 ° C or lower from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The softening point of the phenol resin can be measured by the ring and ball method prescribed in JIS K 6910-2007.

The blending ratio of the epoxy resin to the phenol resin is, for example, suitably adjusted so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitable for 0.8~1.2 equivalents. That is, this is because when the blending ratio of the two is out of the above range, a sufficient curing reaction is not performed, and the properties of the cured epoxy resin are likely to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutadiene. Resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon, or polyamide resin such as 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET, PBT, polyfluorene An amine imimine resin or a fluororesin or the like. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is less ionic impurities, has high heat resistance, and can secure the reliability of a semiconductor wafer is particularly preferable.

A suitable acrylic resin is as described in the first embodiment.

The content of the resin component is preferably 7% by weight or more based on the entire wafer bonding films 303 and 303'. The content of the resin component is preferably 25% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less based on the entire wafer bonding films 303 and 303'.

When the ratio of the thermosetting resin in the resin component (the total amount of the thermosetting resin and the thermoplastic resin) is such that the wafer bonding films 303 and 303' exhibit a function as a thermosetting type when heated under predetermined conditions, there is no particular The limitation is preferably in the range of 75 to 99% by weight, more preferably 85 to 98% by weight, from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The blending ratio of the thermoplastic resin in the resin component is preferably in the range of 1 to 25% by weight, more preferably 2 to 15% by weight, from the viewpoint of improving the fluidity at 120 ° C to 130 ° C.

The wafer bonding films 303, 303' preferably comprise a curing promoting catalyst. Thereby, thermal curing of the epoxy resin and a curing agent such as a phenol resin can be promoted. The curing catalyst is not particularly limited, and examples of the phosphorus-boron-based curing catalyst include tetraphenylboron tetraphenylphosphonium (trade name: TPP-K) and tetrakis(p-tolylboron)tetraphenylphosphonium (product). Name: TPP-MK), triphenylphosphine triphenylborane (trade name: TPP-S), etc. (both manufactured by Beixing Chemical Industry Co., Ltd.). Examples of the imidazole-based curing accelerator (imidazole-based curing acceleration catalyst) include 2-methylimidazole (trade name: 2 MZ), 2-undecylimidazole (trade name: C11-Z), and 2-heptadecane. Imidazole (trade name: C17Z), 1,2-dimethylimidazole (trade name: 1.2DMZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-phenylimidazole (trade name) : 2PZ), 2-phenyl-4-methylimidazole (trade name: 2P4MZ), 1-benzyl-2-methylimidazole (trade name: 1B2MZ), 1-benzyl-2-phenylimidazole (commercial product Name: 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name: 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecylimidazolyl-(1')]- Ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl- S-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid Product (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethylimidazole (trade name: 2P4MHZ-PW), etc. (all manufactured by Shikoku Chemical Industry Co., Ltd.). Among them, from the viewpoint of high reactivity and curing reaction in a short period of time, 2-phenyl-4,5-dihydroxymethylimidazole is preferred.

The content of the curing catalyst can be appropriately set, and is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermosetting resin.

When the wafer bonding films 303 and 303' are crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer is added as a crosslinking agent at the time of production. Just fine. Thereby, the adhesive property at a high temperature can be improved, and the heat resistance can be improved.

A suitable crosslinking agent is as described in the first embodiment.

Further, in the wafer bonding films 303 and 303', a filler other than the thermally conductive particles can be appropriately blended depending on the application. The formulation of the filler can adjust the modulus of elasticity and the like. The specifics of the filler are, for example, the description in the first embodiment.

In the wafer bonding films 303, 303', in addition to the filler, other additives may be appropriately formulated as needed. Specific examples of the other additives are as described in the first embodiment.

The laminated structure of the wafer bonding films 303 and 303' is not particularly limited, and examples thereof include a structure in which only a single layer of the adhesive layer is formed, and a multilayer structure in which an adhesive layer is formed on one or both sides of the core material. . The core material may, for example, be a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a glass. A resin substrate, a ruthenium substrate, a glass substrate, or the like in which a fiber or a plastic non-woven fabric is reinforced.

The thickness of the wafer bonding films 303 and 303' (the total thickness in the case of the laminate) is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. Further, the thickness of the die-bonding films 303 and 303' is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less.

With respect to the substrate 1, the adhesive layer 2, and the die-bonding films 303 and 303', in order to prevent static electricity from being generated during adhesion and peeling, and thereby causing the semiconductor wafer or the like to be charged, the circuit may be broken. The wafer bonding films 310 and 312 with the dicing sheets have an antistatic function. The antistatic function can be performed by adding an antistatic agent or a conductive material to the substrate 1, the adhesive layer 2, the die bond films 303 and 303', and attaching the substrate 1 to the substrate 1 by an appropriate method. A conductive layer made of a charge transfer complex, a metal film, or the like. Among these methods, it is preferable that the impurity ions which may deteriorate the semiconductor wafer are less likely to be generated. In order to impart conductivity Examples of the conductive material (conductive filler) to be used for the purpose of improving conductivity and conductivity include spherical, needle-like, sheet-like metal powders such as silver, aluminum, gold, copper, nickel, and conductive alloys, and amorphous materials. Carbon black, graphite, etc.

The wafer bonding films 303, 303' of the wafer-bonding films 310, 312 with the dicing sheets are preferably protected by a separator (not shown). The separator has a function of providing a protective material for protecting the wafer bonding films 303, 303'. Further, the separator can be further used as a support substrate when the wafer bonding films 303 and 303' are transferred to the adhesive layer 2. The separator is peeled off when the workpiece is bonded to the wafer bonding films 303, 303' of the wafer bonding films 310, 312 to which the dicing sheets are attached. As the separator, a plastic film surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, or a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. , paper, etc.

The wafer bonding films 310 and 312 with the dicing sheets can be manufactured by the method described in the first embodiment or the like.

In the third embodiment, the semiconductor device can be manufactured by the same method as in the first embodiment.

<<Fourth invention>>

The fourth invention will be described here.

The fourth problem to be solved by the invention

In order to make the wafer bonding film highly thermally conductive, it is necessary to mix a high thermal conductivity thermally conductive particle with a large amount of filling. However, in the state in which the thermally conductive particles are largely filled in the wafer bonding film, the surface unevenness of the wafer bonding film is changed. Big. Therefore, there is a problem in that the peeling force at the time of peeling from the state of being laminated on the dicing sheet is locally large or small, and is unstable.

The fourth aspect of the present invention has been made in view of the above-mentioned problems, and an object of the invention is to provide a heat-solid which is capable of reducing the unevenness of the surface and which is capable of stabilizing the peeling force when peeling off from the state of being laminated on the dicing sheet. A wafer bonding film, and a wafer bonding film with a dicing sheet having the thermosetting wafer bonding film.

Further, a method of producing the thermosetting wafer bonding film and a method of manufacturing a semiconductor device using the wafer bonding film with the dicing sheet are provided.

The inventors of the present invention have studied the thermosetting wafer bonding film in order to solve the above conventional problems. As a result, it has been found that the peeling force at the time of peeling from the state laminated on the dicing sheet can be stabilized by adopting the following configuration, and thus the fourth invention has been completed.

That is, the thermosetting die-bonding film of the fourth aspect of the invention is characterized in that it has a thermal conductivity of 12 W/m or more with respect to the entire thermosetting wafer bonding film of 75% by weight or more. The thermally conductive particles of K or more have a surface roughness Ra of one side of 200 nm or less.

According to the foregoing technical composition, the thermal conductivity is more than 75% by weight relative to the entire thermosetting die-bonding film of 12 W/m. The thermal conductive particles of K or more have high thermal conductivity.

In addition, since the surface roughness Ra of one of the surfaces is 200 nm or less, when the surface is bonded to the dicing sheet as the bonding surface, the peeling force at the time of peeling from the dicing sheet can be stabilized. The result is stripping The force is locally reduced, and it is possible to suppress the occurrence of warping or the like. For example, it is possible to prevent water from intruding between the cut sheet and the thermosetting wafer bonding film during cutting.

In the foregoing technical composition, the melt viscosity at 80 ° C is preferably 10,000 Pa. s below.

The melt viscosity at 80 ° C is 10000 Pa. When it is s or less, it can be bonded to the cut sheet in the range of the tolerable temperature of the cut sheet (for example, 90 ° C or less).

Further, in the wafer-bonding film according to the fourth aspect of the invention, the thermosetting wafer-bonding film and the dicing sheet are laminated with the surface roughness Ra being the one surface as a bonding surface.

According to the above-described configuration, since the thermosetting wafer bonding film and the dicing sheet are laminated by using the one surface as a bonding surface, the peeling force when the thermosetting wafer bonding film is peeled off from the dicing sheet can be stabilized. .

Further, a method of manufacturing a thermosetting wafer bonding film according to a fourth aspect of the present invention is characterized in that it is a method of producing the above-described thermosetting type wafer bonding film, comprising the steps of: forming a thermosetting wafer bonding film The adhesive composition solution is coated on the first separator to form a coating film; and the second separator is overlapped on the coating film at a temperature of 40 ° C to 100 ° C and a pressure of 0.1 Pa to 1.0 Pa Under the condition, in the range of 1 to 20 m/min, the first separator and the second separator are sandwiched between the coating film and held to form a thermosetting wafer bonding film.

According to the above-described technical configuration, the first separator and the second separator are sandwiched between the first separator and the second separator at a temperature of 40 to 100 ° C and a pressure of 0.1 Pa to 1.0 Pa at a speed of 1 to 20 m/min. The film is coated and held to form a thermosetting wafer bonding film. Therefore, the aforementioned coating film is planarized between the first separation film and the second separation film. As a result, even if it contains more than 75% by weight or more with respect to the entire thermosetting wafer bonding film, the thermal conductivity is 12 W/m. In the thermally conductive particles of K or more, it is also possible to produce a thermosetting die-bonding film having a small unevenness on the surface and having at least one surface having a surface roughness Ra of 200 nm or less.

Further, a fourth method of manufacturing a semiconductor device of the present invention is characterized in that it comprises the steps of: preparing the above-described wafer-bonding film with a dicing sheet; and thermosetting a wafer of the wafer-bonding film with the dicing sheet a bonding step of bonding the bonding film to the back surface of the semiconductor wafer; cutting the semiconductor wafer together with the thermosetting wafer bonding film to form a wafer-shaped semiconductor wafer; and cutting the semiconductor wafer and the heat a step of picking up the solid wafer bonding film together from the wafer bonding film with the dicing sheet; and a wafer bonding step of bonding the semiconductor wafer wafer to the adherend via the aforementioned thermosetting wafer bonding film.

The wafer-bonding film with a dicing sheet is formed by laminating a thermosetting wafer-bonding film and a dicing sheet with the one surface as a bonding surface. Therefore, when the thermosetting wafer bonding film is peeled off from the dicing sheet, The peeling force is stable. Therefore, the aforementioned pickup step can be stably performed Step.

Hereinafter, the fourth invention will be described in detail with reference to the fourth embodiment, but the fourth invention is not limited thereto.

[Embodiment 4] (wafer bonding film with cut sheet)

The thermosetting wafer bonding film of the fourth embodiment (hereinafter also referred to as "wafer bonding film") and the wafer bonding film with the dicing sheet are described below. In the wafer bonding film of the fourth embodiment, a wafer bonding film in a state in which the dicing sheet is not bonded to the wafer bonding film with a dicing sheet described below is exemplified. Therefore, the wafer bonding film with the dicing sheet will be described below, and the wafer bonding film will be described.

As shown in FIG. 8, the wafer bonding film 410 with a dicing sheet has a structure in which the wafer bonding film 403 is laminated on the dicing sheet 11. The dicing sheet 11 is formed by laminating a binder layer 2 on a substrate 1, and a wafer bonding film 403 is provided on the binder layer 2. The wafer bonding film 403 includes a workpiece attaching portion 403a for attaching a workpiece and a peripheral portion 403b disposed at a periphery of the workpiece attaching portion 403a. As shown in Fig. 9, the modification may be a wafer bonding film 412 having a dicing sheet provided with a wafer bonding film 403' only at a workpiece attaching portion.

The wafer bonding films 403 and 403' have a thermal conductivity of 12 W/m or more with respect to the entire thermosetting wafer bonding film of 75% by weight or more. The thermally conductive particles of K or more are preferably contained in an amount of 80% by weight or more, more preferably 85% by weight or more. In addition, the more the content of the thermally conductive particles is, the better, but The viewpoint of film properties is, for example, 93% by weight or less. The thermal conductivity of the whole of the thermosetting wafer-bonding film is 7 wt% or more and is 12 W/m. In the case of thermally conductive particles of K or more, the semiconductor device manufactured using the thermosetting wafer bonding film is excellent in heat dissipation properties. The thermal conductivity of the thermally conductive particles can be estimated from the crystal structure of the thermally conductive particles obtained by X-ray structural analysis.

The thermal conductivity of the wafer bonding films 403, 403' after heat curing is preferably 1 W/m. K or more, more preferably 1.2 W/m. K or more, and more preferably 1.5W/m. K or more. The thermal conductivity after heat curing is 1W/m. In the case of K or more, the semiconductor device manufactured using the wafer bonding films 403 and 403' is more excellent in heat dissipation properties. The higher the thermal conductivity of the wafer bonding films 403, 403' after heat curing, the better, but for example 20 W / m. Below K.

The "thermal conductivity after heat curing" means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

The surface roughness Ra of one surface of the wafer bonding films 403 and 403' is 200 nm or less. Specifically, when the wafer bonding films 403 and 403' are not laminated with the dicing sheet 11, the surface roughness Ra of at least one surface is 200 nm or less. In this case, when the surface having the surface roughness Ra of 200 nm or less is used as the bonding surface and is bonded to the dicing sheet, the peeling force at the time of peeling from the dicing sheet can be stabilized.

When the wafer bonding films 403 and 403' are laminated on the dicing sheet 11, the surface roughness Ra of the bonding surface with the dicing sheet is 200 nm or less. At this time, the wafer bonding films 403 and 403' and the dicing sheet 11 are formed as a bonding surface with a surface having a surface roughness Ra of 200 nm or less. Since the lamination is performed, the peeling force when the wafer bonding films 403 and 403' are peeled off from the dicing sheet 11 can be stabilized. The surface roughness Ra is preferably 150 nm or less. Further, the surface roughness Ra is preferably as small as possible, but may be, for example, 10 nm or more.

In addition, the melt adhesion at 80 ° C of the wafer bonding film 403, 403 ′ is preferably 10000 Pa. Below s, more preferably 8000Pa. s below, and more preferably 5000Pa. s below. Since the dicing sheet 11 is generally resistant to a temperature of about 90 ° C or less, when the wafer bonding films 403 and 403 ′ are bonded to the dicing sheet 11 , it is necessary to perform bonding under the temperature tolerance of the dicing sheet 11 . Therefore, the melt adhesion of the wafer bonding film 403, 403' at 80 ° C is 10000 Pa. When it is s or less, it can be bonded to the cut sheet in the range of the tolerable temperature (for example, 90 degrees C or less) of the cut sheet 11. Further, it is preferable that the wafer bonding films 403 and 403' have a small melt viscosity at 80 ° C, but from the viewpoint of maintaining the shape of the film, for example, it can be set to 100 Pa. s above. The melt viscosity at 80 ° C is a value obtained by setting the shear rate as a measurement condition to 5 sec ^-1 .

In addition, the melt adhesion of the wafer bonding films 403, 403' at 130 ° C is preferably 10 Pa. s~300Pa. Within the range of s, more preferably 20Pa. s~280Pa. Within the range of s, it is more preferably 50Pa. s~250Pa. Within the scope of s. The melt viscosity at 130 ° C is 10 Pa. s~300Pa. In the range of s, the shape of the film is maintained and the viscosity is low. Therefore, it is possible to sufficiently follow the irregularities of the adherend such as a printed circuit board and suppress the occurrence of voids.

The melt viscosity at 130 ° C is a value obtained by setting the shear rate as a measurement condition to 5 sec ^-1 .

The thermally conductive particles are preferably selected from the group consisting of alumina particles (thermal conductivity: 36 W/m.K), zinc oxide particles (thermal conductivity: 54 W/m.K), and aluminum nitride particles (thermal conductivity: 150 W/m.K). ), cerium nitride particles (thermal conductivity: 27W/m.K), cerium carbide particles (thermal conductivity: 200W/m.K), magnesium oxide particles (thermal conductivity: 59W/m.K), and boron nitride particles (thermal conductivity: 60 W/m.K) at least one particle in the group. In particular, alumina has a high thermal conductivity and is preferred in terms of dispersibility and ease of availability. Further, since boron nitride has a higher thermal conductivity, it can be suitably used.

The thermally conductive particles are preferably treated with a decane coupling agent (pretreatment). Thereby, the dispersibility of the thermal conductive particles is improved, the thermal conductive particles can be sufficiently filled, and the thermal conductivity due to aggregation can be prevented from being lowered. In addition, since the aggregation is suppressed, the surface roughness can be reduced.

A suitable decane coupling agent is as described in the first embodiment.

The method of treating the thermally conductive particles with a decane coupling agent is not particularly limited, and examples thereof include a wet method in which a thermally conductive particle and a decane coupling agent are mixed in a solvent, and a thermally conductive particle and a decane couple in a gas phase. A dry method in which the crosslinking agent is treated.

The treatment amount of the decane coupling agent is not particularly limited, and it is preferred to treat 0.05 to 5 parts by weight of the decane coupling agent with respect to 100 parts by weight of the thermally conductive particles.

The shape of the thermally conductive particles is not particularly limited, and for example, flakes, needles, filaments, spheres, or scaly particles can be used to improve dispersion. In terms of properties and filling ratio, spherical particles are preferred.

The average particle diameter of the thermally conductive particles is preferably 1 μm or more and 10 μm or less, and more preferably 1.5 μm or more and 8 μm or less. By setting the average particle diameter of the thermally conductive particles to 1 μm or more, it is possible to ensure the wettability of the thermosetting wafer-bonding film to the adherend or the semiconductor wafer, and to exhibit good adhesion, which is 10 μm. Hereinafter, the effect of improving thermal conductivity by adding thermally conductive particles can be further improved. Further, by the average particle diameter in the above range, the thickness of the thermosetting wafer-bonding film can be reduced, and the semiconductor wafer can be further laminated, and the thermally conductive particles can be prevented from protruding from the thermosetting wafer bonding film to cause the wafer turtle. The production of cracks. The average particle diameter of the thermally conductive particles is a value obtained by a photometric type particle size distribution meter (manufactured by HORIBA, LTD., device name; LA-910).

Further, as the thermally conductive particles, two or more types of thermally conductive particles having different average particle diameters can be used. This is because the filling rate can be easily increased by using two or more kinds of thermally conductive particles having different average particle diameters.

The laminated structure of the wafer bonding films 403 and 403' is not particularly limited, and examples thereof include a structure in which only a single layer of the adhesive layer is formed, and a multilayer structure in which an adhesive layer is formed on one or both sides of the core material. . Examples of the core material include a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a glass. A resin substrate, a ruthenium substrate, a glass substrate, or the like in which a fiber or a plastic non-woven fabric is reinforced.

The wafer bonding films 403 and 403' preferably contain a resin component such as a thermoplastic resin or a thermosetting resin.

Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. Particularly preferred is an epoxy resin having a small content of ionic impurities such as etching semiconductor wafers. Further, the curing agent for the epoxy resin is preferably a phenol resin.

The epoxy resin is not particularly limited as long as it is generally used as the adhesive composition. For example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol can be used. A type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, trihydroxyphenylmethane type, tetrakis(phenylhydroxy)ethane type and the like An epoxy resin, a polyfunctional epoxy resin; or an epoxy resin such as a carbendazim type, a triglycidyl isocyanurate type or a glycidylamine type. These may be used alone or in combination of two or more. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetrakis(phenylhydroxy)ethane type epoxy resin is particularly preferred. These epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

Further, the epoxy resin may be used in combination with a resin which is solid at normal temperature and a resin which is liquid at normal temperature. By adding an epoxy resin which is liquid at normal temperature to an epoxy resin which is solid at normal temperature, it is possible to improve the fragility at the time of film formation and to improve workability.

Among them, from the viewpoint of being able to lower the melt viscosity at 80 ° C of the thermosetting wafer bonding film, among the above epoxy resins, the softening point is preferably Resin below 80 °C.

The softening point of the epoxy resin can be measured by the ring and ball method prescribed in JIS K 7234-1986.

Further, the phenol resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butyl phenol novolak resin, and a nonylphenol phenol aldehyde. A novolac type phenol resin such as a varnish resin; a polyoxystyrene such as a resol type phenol resin or polyoxy oxy styrene. They may be used singly or in combination of two or more. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

Among these, from the viewpoint of reducing the melt viscosity at 80 ° C of the thermosetting wafer-bonding film, among the phenol resins, a resin having a softening point of 80 ° C or less is preferable.

The softening point of the phenol resin can be measured by the ring and ball method prescribed in JIS K 6910-2007.

The blending ratio of the epoxy resin to the phenol resin is, for example, suitably adjusted so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitably, it is 0.8 to 1.2 equivalents. That is, this is because when the blending ratio of the two is out of the above range, a sufficient curing reaction is not performed, and the properties of the cured epoxy resin are likely to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, and ethylene-vinyl acetate copolymer. Ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon, 6,6-nylon, etc., phenoxy resin Acrylic resin, saturated polyester resin such as PET or PBT, polyamidoximine resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is less excellent in ionic impurities, has high heat resistance, and can secure the reliability of a semiconductor wafer.

A suitable acrylic resin is as described in the first embodiment.

The content of the resin component is preferably 7% by weight or more based on the entire wafer bonding films 403 and 403'. The content of the resin component is preferably 25% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less based on the entire wafer bonding films 403 and 403'.

When the ratio of the thermosetting resin in the resin component (the total amount of the thermosetting resin and the thermoplastic resin) is such that the wafer bonding films 403 and 403' exhibit a function as a thermosetting type when heated under predetermined conditions, there is no particular In order to reduce the melt viscosity at 80 ° C, it is preferably in the range of 75 to 99% by weight, more preferably in the range of 85 to 98% by weight.

Further, the blending ratio of the thermoplastic resin in the resin component is preferably in the range of 1 to 25% by weight, more preferably 2 to 15% by weight, in order to lower the melt viscosity at 80 °C.

The wafer bonding films 403, 403' preferably contain a curing catalyst. Thereby, thermal curing of the epoxy resin and a curing agent such as a phenol resin can be promoted. The curing catalyst is not particularly limited, and examples thereof include tetraphenylboron tetraphenylphosphonium (trade name: TPP-K) and tetrakis(p-tolylboron)tetraphenylphosphonium (Business). Product name: TPP-MK), phosphorus-boron-based curing catalyst such as triphenylphosphine triphenylborane (trade name: TPP-S) (all manufactured by Beixing Chemical Industry Co., Ltd.). Among them, tetrakis(p-tolylboron)tetraphenylphosphonium is preferred from the viewpoint of excellent latent property and good storage stability at room temperature.

The content of the curing catalyst can be appropriately set, and is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermosetting resin.

When the wafer bonding films 403 and 403' are crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer is added as a crosslinking agent at the time of production. Just fine. Thereby, the adhesive property at a high temperature can be improved and the heat resistance can be improved.

A suitable crosslinking agent is as described in the first embodiment.

Further, in the wafer bonding films 403 and 403', a filler other than the above thermally conductive particles can be appropriately blended depending on the application. The formulation of the aforementioned filler can adjust the modulus of elasticity and the like. The specifics of the filler are, for example, the description in the first embodiment.

In the wafer bonding films 403 and 403', in addition to the above-mentioned filler, other additives may be appropriately formulated as needed. Specific examples of the other additives are as described in the first embodiment.

The thickness of the wafer bonding films 403 and 403' (the total thickness in the case of the laminated body) is not particularly limited, and is preferably from the viewpoint of preventing the defect of the cut surface of the wafer and the compatibility of the fixing and holding of the adhesive layer. 1 to 200 μm, more preferably 3 to 100 μm, still more preferably 5 to 80 μm.

The above-mentioned dicing sheet can be used for the purpose of preventing the static electricity from being generated during the adhesion and the peeling of the substrate 1, the adhesive layer, and the wafer bonding film, thereby causing the semiconductor wafer or the like to be charged and causing the circuit to be broken. The wafer bonding films 410 and 412 have an antistatic function. The antistatic function can be performed by adding an antistatic agent or a conductive material to the substrate 1, the adhesive layer 2, the die bond films 403 and 403', and attaching the substrate 1 to the substrate 1 by an appropriate method. A conductive layer made of a charge transfer complex, a metal film, or the like. Among these methods, it is preferred that the impurity ions which are likely to deteriorate the semiconductor wafer are not generated. The conductive material (conductive filler) to be added for the purpose of imparting conductivity, conductivity, and the like may be a spherical, needle-like or sheet-like metal powder such as silver, aluminum, gold, copper, nickel or a conductive alloy. , amorphous carbon black, graphite, etc.

The wafer bonding films 403, 403' of the wafer-bonding films 410, 412 with the dicing sheets are preferably protected by a separator (not shown). The separator has a function of providing a protective material for protecting the wafer bonding films 403, 403'. Further, the separator can be further used as a support substrate when the wafer bonding films 403, 403' are transferred to the adhesive layer 2. The separator is peeled off when the workpiece is bonded to the wafer bonding films 403, 403' of the wafer bonding films 410, 412 to which the dicing sheets are attached. As the separator, a plastic film surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, or a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. , paper, etc.

(Method of Manufacturing Wafer Bonding Film)

The wafer bonding films 403, 403' can be manufactured, for example, as follows.

First, an adhesive composition solution for forming the wafer bonding films 403, 403' is produced. The adhesive composition solution is prepared by dissolving or dispersing a binder composition of a material for forming the wafer bonding films 403 and 403' in a solvent (hereinafter, the solution also includes a dispersion). As described above, the above-mentioned adhesive composition is prepared by thermally conductive particles, a thermosetting resin as needed, a thermoplastic resin, and various other additives.

Next, the above-mentioned adhesive composition solution is applied onto a first separator (not shown) so as to have a predetermined thickness to form a coating film. The coating method is not particularly limited, and examples thereof include roll coating, screen printing coating, gravure coating, and the like.

Next, a second separator (not shown) is placed on the coating film, and the temperature is in the range of 1 m/min to 20 m/min at a temperature of 40 to 100 ° C and a pressure of 0.01 MPa to 1.0 Pa. The first separator and the second separator sandwich the coating film and are held to form the wafer bonding films 403 and 403'. The temperature is preferably from 45 ° C to 95 ° C, more preferably from 50 ° C to 90 ° C. Further, the pressure is more preferably 0.05 Pa to 5 Pa, still more preferably 0.1 Pa to 3 Pa. Further, the aforementioned speed is more preferably 2 to 15 m/min, and still more preferably 3 to 10 m/min.

The coating film is sandwiched between the first separator and the second separator at a temperature of 40 ° C to 100 ° C and a pressure of 0.1 Pa to 1.0 Pa at a speed of 1 to 20 m/min. The wafer bonding films 403, 403' are formed, and thus the aforementioned coating film is planarized between the first isolation film and the second isolation film. That is, a part of the heat conduction is protruded on the surface of the coated film. The particles are pressed into the film of the wafer bonding films 403 and 403' by pressurization, and the surface is flattened. As a result, even if it contains more than 75% by weight or more with respect to the entire wafer bonding film, the thermal conductivity is 12 W/m. In the thermally conductive particles of K or more, the wafer bonding films 403 and 403' having a small surface unevenness and having at least one surface having a surface roughness Ra of 200 nm or less can be produced.

(Method of Manufacturing Wafer Bonding Film with Cut Sheet)

The wafer bonded films 410 and 412 of the dicing sheet of the present embodiment can be produced, for example, as follows.

First, the substrate 1 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calender film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T die extrusion method, a coextrusion method, a dry lamination method, and the like. .

Next, a coating film is applied onto the substrate 1 to form a coating film, and then the coating film is dried under predetermined conditions (heating is crosslinked as necessary) to form a binder layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen printing coating, gravure coating, and the like. Further, the drying conditions are carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Alternatively, the coating film may be formed by applying a binder to the separator and forming a coating film, and then drying the coating film under the drying conditions to form the binder layer 2. Thereafter, the adhesive layer 2 is bonded to the substrate 1 together with the separator. Thereby, the cut sheet 11 is produced.

Next, the separator sheet 11 and the dicing film 3, 3' are separately peeled off. The film is peeled off so that the dicing films 3 and 3' and the adhesive layer 2 of the dicing sheet 11 are bonded to each other. At this time, the surface having the surface roughness Ra of the wafer bonding films 403 and 403' of 100 nm or less is bonded to the bonding surface of the dicing sheet 11 (adhesive layer 2). The bonding can be performed, for example, by crimping. In this case, the lamination temperature is not particularly limited, and is, for example, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.1 to 20 kgf/cm, more preferably 1 to 10 kgf/cm. Next, the base material separator on the adhesive layer is peeled off to obtain the wafer bonded films 410 and 412 of the cut sheet of the present embodiment.

In the fourth embodiment, the semiconductor device can be manufactured by the same method as in the first embodiment. In the fourth embodiment, since the wafer bonding film 403 and the dicing sheet 11 are bonded to each other with the surface having the surface roughness Ra of 100 nm or less as the bonding surface, the peeling force when the wafer bonding film 403 is peeled off from the dicing sheet 11 can be removed. stable. Therefore, the pickup step can be surely performed. Further, the peeling force is locally reduced, and occurrence of warpage or the like can be suppressed. For example, it is possible to prevent water from entering between the dicing sheet 11 and the wafer bonding film 403 at the time of dicing.

<<The fifth invention>>

The fifth invention will be described here.

Problem to be solved by the fifth invention

In order to make the wafer bonding film highly thermally conductive, it is necessary to mix a high thermal conductivity thermally conductive particle with a large amount of filling. However, in a state in which a large amount of thermally conductive particles are filled in the wafer bonding film, there are the following problems: thermal conductive particles The interaction with the resin increases the viscosity of the die bond film, so that the fluidity is lowered and it is difficult to attach to the semiconductor wafer.

The fifth invention has been made in view of the above problems, and an object thereof is to provide a method of manufacturing a semiconductor device capable of easily attaching a thermosetting wafer bonding film to a semiconductor wafer.

The inventors of the present invention have studied the method of manufacturing a semiconductor device in order to solve the above conventional problems. As a result, it has been found that the thermosetting die-bonding film can be easily attached to the semiconductor wafer by the following technical configuration, and thus the fifth invention has been completed.

In the method of manufacturing a semiconductor device according to a fifth aspect of the present invention, in the step of preparing a thermosetting wafer bonding film, the thermosetting wafer bonding film contains 75% by weight or more based on the entire thermosetting wafer bonding film. The thermal conductivity is 12W/m. The thermal conductive particles above K, the thermal conductivity after heat curing is 1W/m. Above K, the melt viscosity at 80 ° C is 5000 Pa. s or less; and a bonding step of bonding the thermosetting die-bonding film to the back surface of the semiconductor wafer at a temperature of 80 ° C or lower and a pressure of 1.0 MPa or less.

According to the foregoing technical configuration, the thermosetting wafer bonding film has a thermal conductivity of 12 W/m or more with respect to the entire thermosetting wafer bonding film of 75% by weight or more. The thermal conductive particles above K, the thermal conductivity of the thermosetting wafer bonding film after thermal curing is 1 W / m. Above K, it has high thermal conductivity.

In addition, the aforementioned thermosetting wafer bonding film has a melt viscosity of 5,000 Pa at 80 ° C. Below s, it is low viscosity even at lower temperatures. Therefore, in the bonding step, even if the thermosetting die-bonding film and the back surface of the semiconductor wafer are bonded at a temperature of 80 ° C or lower and a pressure lower than 1.0 MPa, the film can be reliably bonded. . Since the thermosetting wafer-bonding film can be bonded to the back surface of the semiconductor wafer at a low pressure, it is possible to suppress cracking of the wafer during fixing, which is excellent. Since the wafer is easily cracked as the wafer is thinned year by year, when the wafer is fixed under high pressure, the risk of cracking of the wafer becomes high.

In the above-described technical configuration, it is preferable that the bonding in the bonding step is performed at a bonding speed of 5 to 20 mm/sec.

When the bonding in the bonding step is performed at a faster speed of the bonding speed of 5 to 20 mm/sec, the productivity is improved.

Further, a method of manufacturing a semiconductor device according to a fifth aspect of the present invention is characterized by the step of preparing a wafer-bonding film with a dicing sheet on which a thermosetting wafer bonding film is laminated on a dicing sheet, the thermosetting wafer bonding film containing a relative The thermal conductivity of the thermosetting wafer bonding film is 75 wt% or more and the thermal conductivity is 12 W/m. The thermal conductive particles above K, the thermal conductivity after heat curing is 1W/m. Above K, the melt viscosity at 80 ° C is 5000 Pa. s or less; and a bonding step of bonding the thermosetting wafer bonding film of the wafer-bonding film of the dicing sheet to the back surface of the semiconductor wafer at a temperature of 80 ° C or lower and a pressure of 1.0 MPa or less.

According to the foregoing technical configuration, the thermosetting wafer bonding film contains a thermal conductivity of 7W/m or more with respect to the entire thermosetting wafer bonding film of 75% by weight or more. The thermal conductive particles above K, the thermal conductivity of the thermosetting wafer bonding film after thermal curing is 1 W / m. Above K, it has high thermal conductivity.

In addition, the aforementioned thermosetting wafer bonding film has a melt viscosity of 5,000 Pa at 80 ° C. Below s, it is low viscosity even at lower temperatures. Therefore, in the bonding step, even if the thermosetting wafer bonding film and the back surface of the semiconductor wafer are bonded at a temperature of 80 ° C or lower and a pressure of 1.0 MPa or less, the bonding can be surely bonded. Since the thermosetting wafer bonding film can be bonded to the back surface of the semiconductor wafer at a low pressure, it is excellent in that it is less likely to cause wafer cracking due to pressure.

Further, since the thermosetting wafer bonding film is laminated on the dicing sheet in advance, the step of attaching the thermosetting wafer bonding film to the dicing sheet can be omitted.

In the above-described technical configuration, it is preferable that the bonding in the bonding step is performed at a bonding speed of 5 to 20 mm/sec.

When the bonding in the bonding step is performed at a faster speed of the bonding speed of 5 to 20 mm/sec, the productivity is improved.

Hereinafter, the fifth invention will be described in detail with reference to the fifth embodiment, but the fifth invention is not limited thereto.

[Embodiment 5] (wafer bonding film with cut sheet)

The thermosetting wafer bonding film of the fifth embodiment (hereinafter also referred to as "wafer bonding film") and the wafer bonding film with the dicing sheet are described below. In the wafer bonding film of the fifth embodiment, a wafer bonding film in a state in which the dicing sheet is not bonded to the wafer bonding film with a dicing sheet described below is exemplified. Therefore, the wafer bonding film with the dicing sheet will be described below, and the wafer bonding film will be described.

As shown in FIG. 10, the wafer bonding film 510 with a dicing sheet has a structure in which a wafer bonding film 503 is laminated on the dicing sheet 11. The dicing sheet 11 is formed by laminating a binder layer 2 on a substrate 1, and a wafer bonding film 503 is provided on the binder layer 2. The wafer bonding film 503 includes a workpiece attaching portion 503a for attaching a workpiece and a peripheral portion 503b disposed at a periphery of the workpiece attaching portion 503a. As shown in Fig. 11, the modification may be a wafer bonding film 512 provided with a dicing sheet of the wafer bonding film 503' only at the workpiece attaching portion.

The thermal conductivity of the wafer bonding films 503, 503' after heat curing is 1 W/m. K or more, preferably 1.2 W/m. K or more, more preferably 1.5W/m. K or more. The thermal conductivity after heat curing is 1W/m. Since K is more than the above, the semiconductor device manufactured using the wafer bonding films 503 and 503' is excellent in heat dissipation. The higher the thermal conductivity of the wafer bonding films 503, 503', the better, but for example 20 W/m. Below K.

The "thermal conductivity after heat curing" means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

The wafer bonding films 503, 503' contain a thermal conductivity of 12 W/m or more with respect to the entire thermosetting wafer bonding film of 75% by weight or more. K or more The thermally conductive particles preferably contain 80% by weight or more, more preferably 85% by weight or more. In addition, the content of the heat conductive particles is preferably as large as possible, but is, for example, 93% by weight or less from the viewpoint of film formability. The thermal conductivity of the whole of the thermosetting wafer-bonding film is 7 wt% or more and is 12 W/m. In the case of the thermal conductive particles of K or more, the semiconductor device manufactured using the thermosetting wafer bonding film is more excellent in heat dissipation properties. The thermal conductivity of the thermally conductive particles can be estimated from the crystal structure of the thermally conductive particles obtained by X-ray structural analysis.

Further, the wafer bonding films 503, 503' have a melt viscosity at 80 ° C of 5000 Pa. Below s, preferably 2000 Pa. Below s, more preferably 1200Pa. s below. Further, the smaller the melt viscosity at 80 ° C, the better, but from the viewpoint of maintaining the shape of the film, for example, it can be set to 500 Pa. s above. The wafer bonding films 503, 503' have a melt viscosity at 80 ° C of 5000 Pa. Below s, it is low viscosity even at lower temperatures. Therefore, in the bonding step (the step of bonding the wafer bonding film to the back surface of the semiconductor wafer) to be described later, the wafer bonding films 503 and 503' and the back surface of the semiconductor wafer are at a temperature of 80 ° C or lower and 0.2. The bonding can be carried out at a lower pressure of MPa or less, and it can be reliably bonded. Since the wafer bonding films 503 and 503' can be bonded to the back surface of the semiconductor wafer at a low pressure, wafer cracking due to pressure is less likely to occur, which is superior in this respect.

In addition, the melt adhesion of the wafer bonding film 503, 503' at 130 ° C is preferably 10 Pa. s~300Pa. Within the range of s, preferably 20 Pa. s~280Pa. Within the range of s, more preferably 50Pa. s~250Pa. Within the scope of s. The melt viscosity at 130 ° C is 10 Pa. s~300Pa. In the range of s, the shape of the film is maintained and the viscosity is low. Therefore, it is possible to sufficiently follow the irregularities of the adherend such as a printed circuit board, and it is possible to suppress the occurrence of voids. The melt viscosity at 130 ° C is a value obtained by setting the shear rate as a measurement condition to 5 sec ^-1 .

The thermally conductive particles are preferably selected from the group consisting of alumina particles (thermal conductivity: 36 W/m.K), zinc oxide particles (thermal conductivity: 54 W/m.K), and aluminum nitride particles (thermal conductivity: 150 W/m.K). ), cerium nitride particles (thermal conductivity: 27W/m.K), cerium carbide particles (thermal conductivity: 200W/m.K), magnesium oxide particles (thermal conductivity: 59W/m.K), and boron nitride particles (thermal conductivity: 60 W/m.K) at least one particle in the group. In particular, alumina has a high thermal conductivity and is preferred in terms of dispersibility and ease of availability. Further, since boron nitride has a higher thermal conductivity, it can be suitably used.

The thermally conductive particles are preferably treated with a decane coupling agent (pretreatment). Thereby, the dispersibility of the thermal conductive particles is improved, and the thermally conductive particles can be sufficiently filled.

A suitable decane coupling agent is as described in the first embodiment.

The method of treating the thermally conductive particles with a decane coupling agent is not particularly limited, and examples thereof include a wet method in which a thermally conductive particle and a decane coupling agent are mixed in a solvent, and a coupling of a thermally conductive particle and a decane in a gas phase. Dry method for treating the agent.

The treatment amount of the decane coupling agent is not particularly limited, and it is preferred to treat 0.05 to 5 parts by weight of the decane coupling agent with respect to 100 parts by weight of the thermally conductive particles.

The shape of the heat conductive particles is not particularly limited, and for example, it can be made The particles in the form of flakes, needles, filaments, spheres, and scales are preferably spherical particles from the viewpoint of improving dispersibility and filling ratio.

The average particle diameter of the thermally conductive particles is preferably 1 μm or more and 10 μm or less, and more preferably 1.5 μm or more and 8 μm or less. By setting the average particle diameter of the heat conductive particles to 1 μm or more, it is possible to ensure the wettability of the thermosetting wafer bonded film to the adherend or the semiconductor wafer, and to exhibit good adhesion, which is 10 μm. Hereinafter, the effect of improving thermal conductivity by adding thermally conductive particles can be further improved. Further, by the average particle diameter in the above range, the thickness of the thermosetting wafer-bonding film can be reduced, and the semiconductor wafer can be further laminated, and the thermally conductive particles can be prevented from protruding from the thermosetting wafer bonding film to cause the wafer turtle. The production of cracks. The average particle diameter of the thermally conductive particles is a value obtained by a photometric type particle size distribution meter (manufactured by HORIBA, LTD., device name; LA-910).

Further, as the thermally conductive particles, two or more types of thermally conductive particles having different average particle diameters can be used. This is because the filling rate can be easily increased by using two or more kinds of thermally conductive particles having different average particle diameters.

The laminated structure of the die-bonding films 503 and 503' is not particularly limited, and examples thereof include a structure in which only a single layer of the adhesive layer is formed, and a multilayer structure in which an adhesive layer is formed on one or both sides of the core material. . Examples of the core material include a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a glass. A resin substrate, a ruthenium substrate, a glass substrate, or the like in which a fiber or a plastic non-woven fabric is reinforced.

The wafer bonding films 503, 503' preferably comprise a thermoplastic resin, a thermoset A resin component such as a resin.

Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. Particularly preferred is an epoxy resin having a small content of ionic impurities such as etching semiconductor wafers. Further, the curing agent for the epoxy resin is preferably a phenol resin.

The epoxy resin is not particularly limited as long as it is generally used as a binder, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A can be used. Type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, trishydroxyphenylmethane type, tetrakis(phenylhydroxy)ethane type and the like Resin, polyfunctional epoxy resin; or epoxy resin such as carbendazim type, triglycidyl isocyanurate type or glycidylamine type. They may be used singly or in combination of two or more. Among these epoxy resins, a particularly preferred novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetrakis(phenylhydroxy)ethane type epoxy resin. These epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

Further, the epoxy resin may be used in combination with a resin which is solid at normal temperature and a resin which is liquid at normal temperature. By adding an epoxy resin which is liquid at normal temperature to an epoxy resin which is solid at normal temperature, it is possible to improve the fragility at the time of film formation and to improve workability.

Among them, from the viewpoint of being able to lower the melt viscosity at 80 ° C of the thermosetting wafer bonding film, among the above epoxy resins, the softening point is preferably Resin below 80 °C.

The softening point of the epoxy resin can be measured by the ring and ball method prescribed in JIS K 7234-1986.

Further, the phenol resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butyl phenol novolak resin, and a nonylphenol phenol aldehyde. A novolac type phenol resin such as a varnish resin; a polyoxystyrene such as a resol type phenol resin or polyoxy oxy styrene. These may be used alone or in combination of two or more. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

Among these, from the viewpoint of reducing the melt viscosity at 80 ° C of the thermosetting wafer-bonding film, among the phenol resins, a resin having a softening point of 80 ° C or less is preferable.

The softening point of the phenol resin can be measured by the ring and ball method prescribed in JIS K 6910-2007.

The blending ratio of the epoxy resin to the phenol resin is, for example, suitably adjusted so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitably, it is 0.8 to 1.2 equivalents. That is, this is because when the blending ratio of the two is out of the above range, a sufficient curing reaction is not performed, and the properties of the cured epoxy resin are likely to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, and ethylene-vinyl acetate copolymer. Ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon, 6,6-nylon, etc., phenoxy resin Acrylic resin, saturated polyester resin such as PET or PBT, polyamidoximine resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is less excellent in ionic impurities, has high heat resistance, and can secure the reliability of a semiconductor wafer.

A suitable acrylic resin is as described in the first embodiment.

The content of the resin component is preferably 7% by weight or more based on the entire wafer bonding films 503 and 503'. The content of the resin component is preferably 25% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less based on the entire wafer bonding films 503 and 503'.

When the ratio of the thermosetting resin in the resin component (the total amount of the thermosetting resin and the thermoplastic resin) is such that the wafer bonding films 503 and 503' exhibit a function as a thermosetting type when heated under predetermined conditions, there is no particular In order to reduce the melt viscosity at 80 ° C, it is preferably in the range of 75 to 99% by weight, more preferably in the range of 85 to 98% by weight.

Further, the blending ratio of the thermoplastic resin in the resin component is preferably in the range of 1 to 25% by weight, more preferably 2 to 15% by weight, in order to lower the melt viscosity at 80 °C.

The wafer bonding films 503, 503' preferably contain a curing catalyst. Thereby, thermal curing of the epoxy resin and a curing agent such as a phenol resin can be promoted. The curing catalyst is not particularly limited, and examples thereof include tetraphenylboron tetraphenylphosphonium (trade name: TPP-K) and tetrakis(p-tolylboron)tetraphenylphosphonium (Business). Product name: TPP-MK), phosphorus-boron-based curing catalyst such as triphenylphosphine triphenylborane (trade name: TPP-S) (all manufactured by Beixing Chemical Industry Co., Ltd.). Among them, tetrakis(p-tolylboron)tetraphenylphosphonium is preferred from the viewpoint of excellent latent property and good storage stability at room temperature.

The content of the curing catalyst can be appropriately set, and is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermosetting resin.

When the wafer bonding films 503 and 503' are crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer is added as a crosslinking agent at the time of production. Just fine. Thereby, the adhesive property at a high temperature can be improved, and the heat resistance can be improved.

A suitable crosslinking agent is as described in the first embodiment.

Further, in the wafer bonding films 503 and 503', a filler other than the above thermally conductive particles can be appropriately prepared depending on the application. The formulation of the aforementioned filler can adjust the modulus of elasticity and the like. Specific examples of the filler are as described in the first embodiment.

In the wafer bonding films 503 and 503', in addition to the above-mentioned filler, other additives may be appropriately formulated as needed. Specific examples of the other additives are as described in the first embodiment.

The thickness of the wafer bonding films 503 and 503' (the total thickness in the case of the laminated body) is not particularly limited, and is preferably from the viewpoint of preventing the defect of the wafer-cut surface and the compatibility of the fixing and holding of the adhesive layer. 1 to 200 μm, more preferably 3 to 100 μm, still more preferably 5 to 80 μm.

The wafer bonding films 510 and 512 with the dicing sheets can be manufactured by the method described in the first embodiment or the like.

(Method of Manufacturing Semiconductor Device)

In the method of manufacturing a semiconductor device according to the fifth embodiment, a method of manufacturing a semiconductor device according to the embodiment 5-1 and a method of manufacturing the semiconductor device according to the embodiment 5-2 will be described.

The method of manufacturing a semiconductor device according to Embodiment 5-1 includes the step of preparing a thermosetting wafer bonding film containing 75% by weight or more of heat relative to the entire thermosetting wafer bonding film. The coefficient is 12W/m. The thermal conductivity particles above K have a thermal conductivity of 1 W/m after heat curing. Above K, the melt viscosity at 80 ° C is 5000 Pa. s or less; and a bonding step of bonding the thermosetting die-bonding film to the back surface of the semiconductor wafer at a temperature of 80 ° C or lower and a pressure of 1.0 MPa or less.

The method of manufacturing a semiconductor device according to Embodiment 5-2 includes the step of preparing a wafer-bonded film of a dicing sheet having a thermosetting wafer bonding film laminated on a dicing sheet, the thermosetting wafer bonding film containing heat relative to heat The solid wafer bonding film has a thermal conductivity of more than 75% by weight and a thermal conductivity of 12 W/m. The thermal conductivity particles above K have a thermal conductivity of 1 W/m after heat curing. Above K, the melt viscosity at 80 ° C is 5000 Pa. s Hereinafter, a bonding step of bonding the thermosetting wafer bonding film of the wafer-bonding film of the dicing sheet to the back surface of the semiconductor wafer at a temperature of 80 ° C or lower and a pressure of 1.0 MPa or less is used.

In the method of manufacturing a semiconductor device according to Embodiment 5-2, a wafer bonding film with a dicing sheet is used, and in the method of manufacturing a semiconductor device according to Embodiment 5-1, a wafer bonding film is used as a single body. Different, other aspects are common. In the method of manufacturing a semiconductor device of the embodiment 5-1, when the wafer bonding film is prepared and then bonded to the dicing sheet, the method of manufacturing the semiconductor device of the embodiment 5-2 can be used. Therefore, a method of manufacturing the semiconductor device of the embodiment 5-2 will be described below.

First, a wafer bonding film with a dicing sheet is prepared (preparation step). The wafer bonding films 510, 512 with the dicing sheets can be appropriately peeled off from the arbitrarily disposed separators on the wafer bonding films 503, 503' and used as follows. Hereinafter, a case where the wafer bonding film 510 with a dicing sheet is used will be described as an example with reference to FIG.

First, the semiconductor wafer 4 is bonded to the semiconductor wafer attaching portion 503a of the wafer bonding film 503 in the wafer bonding film 510 with the dicing sheet, and the wafer bonding film 503 is bonded to the back surface of the semiconductor wafer 4. Step by step). This step can be performed, for example, by pressing with a pressing means such as a pressure roller. The bonding temperature at the time of bonding is 80 ° C or lower, preferably 75 ° C or lower. Further, the bonding temperature at the time of bonding may be, for example, 40 ° C or higher. In addition, the pressure at the time of bonding is 1.0 MPa. Lower, preferably 0.15 MPa or less. Further, the pressure at the time of bonding may be, for example, 0.05 MPa or more. As described above, the wafer bonding film 503 has a melt viscosity at 80 ° C of 5000 Pa. Below s, even at lower temperatures, it is low viscosity. Therefore, in this bonding step, even if the wafer bonding film 503 and the back surface of the semiconductor wafer 4 are bonded at a temperature of 80 ° C or lower and a low pressure of 1.0 MPa or less, the bonding can be reliably performed. Since the wafer bonding film 503 can be bonded to the back surface of the semiconductor wafer 4 at a low pressure, even a thin wafer (for example, a wafer of 50 μm or less) is less likely to cause cracks due to pressure, which is excellent. .

Further, the bonding speed at the time of bonding is preferably 5 to 20 mm/sec, more preferably 10 to 15 mm/sec. When the bonding speed is performed at a relatively fast speed of 5 to 20 mm/sec, the productivity is improved.

Next, the semiconductor wafer 4 is cut (cutting step). Thereby, the semiconductor wafer 4 is cut into a predetermined size and singulated to manufacture the semiconductor wafer 5. The method of cutting is not particularly limited, and is performed, for example, from the circuit surface side of the semiconductor wafer 4 in accordance with a conventional method. Further, in this step, for example, a cutting method called a full cut, or the like, which is performed until the wafer bonding film 510 having the dicing sheet is cut, may be employed. The cutting device used in this step is not particularly limited, and a conventionally known device can be used. Further, since the semiconductor wafer is bonded and fixed by the wafer bonding film 510 to which the dicing sheet is attached, wafer defects and wafer scattering can be suppressed, and damage of the semiconductor wafer 4 can be suppressed.

Next, picking up of the semiconductor wafer 5 is performed in order to peel off the semiconductor wafer bonded and fixed to the wafer bonding film 510 to which the dicing sheet is attached (pickup step). The method of picking up is not particularly limited, and various conventionally known methods can be employed. For example, a method in which each of the semiconductor wafers 5 is lifted up by a needle from the wafer bonding film 510 side of the dicing sheet, and the semiconductor wafer 5 that is lifted up is picked up by a pick-up device.

The picking condition is preferably from 5 to 100 mm/sec, more preferably from 5 to 10 mm/sec, from the viewpoint of preventing fragmentation.

Here, when the adhesive layer 2 is an ultraviolet curing type, picking up is performed after irradiating the adhesive layer 2 with ultraviolet rays. Thereby, the adhesive force of the adhesive layer 2 to the wafer bonding film 503 is lowered, and the peeling of the semiconductor wafer 5 becomes easy. As a result, pickup can be performed without damaging the semiconductor wafer 5. The conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be appropriately set as necessary. Further, as the light source used for ultraviolet irradiation, the aforementioned light source can be used. When the adhesive layer is previously irradiated with ultraviolet rays to be cured, and the cured adhesive layer is bonded to the wafer bonding film, ultraviolet irradiation is not required here.

Next, the picked semiconductor wafer 5 is bonded and fixed to the adherend 6 via the wafer bonding film 503 (wafer bonding step). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, or a separately fabricated semiconductor wafer. The adherend 6 may be, for example, a deformed adherend that is easily deformed, or a non-deformable adherend that is not easily deformed (a semiconductor wafer or the like).

As the substrate, a conventionally known substrate can be used. In addition, as the lead frame, a metal lead frame such as a Cu lead frame, a 42 alloy lead frame, a glass epoxy resin, or a BT (Bismaleimide-- An organic substrate made of triazine or polyimine. However, the substrate is not limited thereto, and includes a circuit board that can be used to fix the semiconductor wafer and electrically connect the semiconductor wafer.

Next, since the wafer bonding film 503 is a thermosetting type, the semiconductor wafer 5 is bonded and fixed to the adherend 6 by heat curing, and the heat resistance is improved (thermal curing step). It can be carried out at a heating temperature of 80 to 200 ° C, preferably 100 to 175 ° C, more preferably 100 to 140 ° C. Further, it can be carried out at a heating time of 0.1 to 24 hours, preferably 0.1 to 3 hours, more preferably 0.2 to 1 hour. In addition, heat curing can be carried out under pressurized conditions. The pressurization condition is preferably in the range of 1 to 20 kg/cm ² , more preferably in the range of 3 to 15 kg/cm ² . The heat curing under pressure can be performed, for example, in a chamber filled with an inert gas. In the case of performing thermal curing under pressure, if a void is formed between the wafer bonding film and the adherend in the wafer bonding step, it is dispersed in the resin and disappears in appearance without Swell. As a result, the influence caused by the void can be reduced. The product in which the semiconductor wafer 5 is bonded and fixed on the substrate or the like via the wafer bonding film 503 is available for the reflow step.

The shear adhesive strength of the wafer bonded film 503 after heat curing is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa with respect to the adherend 6 . When the shear bonding strength of the wafer bonding film 503 is at least 0.2 MPa or more, the wafer bonding film 503 and the semiconductor wafer 5 or the adherend 6 are not caused by ultrasonic vibration or heating in this step during the wire bonding step. The bonding surface produces shear deformation. That is, the semiconductor wafer is not moved by the ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of wire bonding from being lowered.

Next, as shown in FIG. 12, the tip end of the terminal portion (internal lead) of the adherend 6 and the electrode pad (not shown) on the semiconductor wafer 5 are electrically connected by the bonding wire 7 (wire bonding step). ). As the bonding wire 7, the gold wire, the aluminum wire, the copper wire, or the like can be used, for example. The temperature at the time of wire bonding can be carried out in the range of 80 to 250 ° C, preferably 80 to 220 ° C. In addition, the heating time can be carried out in a few seconds to several minutes. The wire connection can be performed by using the ultrasonic wave-based vibration energy and the pressure-based pressure-bonding energy in combination in a state of being heated to the aforementioned temperature range. This step can be carried out without performing thermal curing of the wafer bonding film 503. Further, in the process of this step, the semiconductor wafer 5 and the adherend 6 are not fixed by the wafer bonding film 503.

Next, as needed, as shown in FIG. 12, the semiconductor wafer 5 is packaged by the encapsulating resin 8 (packaging step). This step is performed to protect the semiconductor wafer 5 mounted on the adherend 6 and the bonding leads 7. This step can be carried out by molding a resin for encapsulation with a mold. As the encapsulating resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin encapsulation is usually 60 to 90 seconds at 175 ° C. However, the heating conditions are not limited thereto, and for example, it may be cured at 165 to 185 ° C for several minutes. Thereby, the encapsulating resin is cured and the semiconductor wafer 5 and the adherend 6 are fixed via the wafer bonding film 503. In other words, even when the post-cure step to be described later is not performed, the wafer bonding film 503 can be fixed in this step, which contributes to a reduction in the number of manufacturing steps and a shortened manufacturing period of the semiconductor device. Further, in the packaging step, a method of embedding the semiconductor wafer 5 in a sheet-like package sheet may be employed (for example, refer to JP-A-2013- Bulletin No. 7028).

Next, heating is performed as needed to completely cure the encapsulating resin 8 which is not sufficiently cured in the above-described encapsulation step (post-cure step). Even in the case where the wafer bonding film 503 is not completely thermally cured in the encapsulating step, the wafer bonding film 503 can be completely thermally cured together with the encapsulating resin 8 in this step. The heating temperature in this step varies depending on the type of the encapsulating resin, and is, for example, in the range of 165 to 185 ° C, and the heating time is about 0.5 to 8 hours.

After the pre-fixing by the wafer bonding step, wire bonding may be performed without a thermal curing step by heat treatment based on the wafer bonding film 503, and the semiconductor wafer 5 may be encapsulated with a sealing resin, and the encapsulating resin may be cured ( After curing). At this time, the shear adhesive strength at the time of pre-fixing of the wafer bonding film 503 is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa with respect to the adherend 6 . When the shear bonding strength at the time of pre-fixing of the wafer bonding film 503 is at least 0.2 MPa or more, the wafer bonding film 503 is not subjected to ultrasonic vibration or heating in this step even if the wire bonding step is not performed through the heating step. Shear deformation occurs with the bonding surface of the semiconductor wafer 5 or the adherend 6. That is, the semiconductor wafer is not moved by the ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of the wire bonding from being lowered. The pre-fixing state refers to a state in which the wafer bonding film is cured to such an extent that the curing reaction of the thermosetting wafer bonding film is not completed (in a semi-cured state) and the semiconductor wafer is not affected in order to affect the subsequent steps. 5 fixed state. In the case of performing a wire bonding without a heat curing step by a heat treatment based on a wafer bonding film, the above-described post-curing step corresponds to the heat curing step in the present specification.

The wafer-bonding film with a dicing sheet according to the first to fifth aspects of the present invention can also be suitably used in the case where a plurality of semiconductor wafers are stacked and three-dimensionally mounted. In this case, the wafer bonding film and the spacer may be laminated between the semiconductor wafers, or only the wafer bonding film may be laminated between the semiconductor wafers without laminating the spacers, and may be appropriately changed depending on the manufacturing conditions, applications, and the like.

Example <<First embodiment of the invention>>

Hereinafter, suitable embodiments of the first invention will be described in detail by way of examples. However, the materials, the amount of the preparation, and the like described in the examples are not particularly limited, and the gist of the first invention is not limited thereto.

The components used in the examples will be described.

Epoxy Resin 1: JER827 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, liquid at 25 ° C, softening point: less than 25 ° C)

Epoxy Resin 2: KI-3000 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (cresol novolac type epoxy resin, epoxy equivalent: 199 g/eq., softening point: 64 ° C)

Phenolic resin: MEH-7851-SS manufactured by Minghe Chemical Co., Ltd. (phenolic resin having a biphenyl aralkyl skeleton, hydroxyl equivalent: 203 g/eq., softening point: 67 ° C)

Acrylic rubber: TEISANRESIN SG-P3 manufactured by Nagase ChemteX Corporation (acrylic acid copolymer, Mw: 850,000, glass transition temperature: 12 ° C)

Catalyst: TPP-MK manufactured by Beixing Chemical Industry Co., Ltd. (four (p-tolyl boron) tetraphenylphosphonium)

Filler 1: DAW-03 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 5.1 μm, specific surface area: 0.5 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.9)

Filler 2: AO802 manufactured by Admatechs Co., Ltd. (spherical alumina filler, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.95)

Hydrane coupling agent: Table 1

The surface treatment method of the filler will be described.

20 parts by weight of the filler 2 was mixed with 80 parts by weight of the filler 1. The mixture of the filler 1 and the filler 2 was treated with the decane coupling agent described in Table 1 to obtain surface-treated fillers 1 to 7. The surface treatment is carried out by a dry method, and the amount of the decane coupling agent shown in the following formula is treated.

Handling amount of decane coupling agent = (weight of filler (g) × specific surface area of filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

[Examples 1 to 7] Fabrication of wafer bonding film

According to the blending ratio described in Table 2, an epoxy resin, a phenol resin, an acrylic rubber, a catalyst, and a surface-treated filler were dissolved and dispersed in methyl ethyl ketone (MEK) to obtain a viscosity-sensitive adhesive composition solution. Thereafter, the adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxyalkylene release treatment. Then, it was dried at 130 ° C for 2 minutes to obtain a wafer bonded film (thickness 25 μm).

[Comparative Examples 1 to 2] Fabrication of wafer bonding film

According to the compounding ratio described in Table 2, an epoxy resin, a phenol resin, an acrylic rubber, a catalyst, and a filler were dissolved and dispersed in methyl ethyl ketone (MEK) to obtain a viscosity-sensitive adhesive composition solution. Thereafter, the adhesive composition solution was applied onto a release-treated film (release liner) made of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxyalkylene release treatment. Then, it was dried at 130 ° C for 2 minutes to obtain a wafer bonded film (thickness 25 μm).

[Comparative Example 3] Fabrication of wafer bonding film

According to the compounding ratio described in Table 2, an epoxy resin, a phenol resin, an acrylic rubber, a catalyst, a filler, and a decane coupling agent are dissolved and dispersed in methyl ethyl ketone (MEK) to obtain a viscosity-sensitive adhesive composition solution. . Thereafter, the adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxyalkylene release treatment. Then, it was dried at 130 ° C for 2 minutes to obtain a wafer bonded film (thickness 25 μm).

[Evaluation]

The obtained wafer bonded film was evaluated as follows. The results are shown in Table 2.

(filler dispersibility)

A section of 50 mm × 50 mm × 25 μm in thickness was cut out from the wafer bonding film, and the section was measured by transmitted light using an optical microscope to confirm the presence or absence of aggregates. The portion where the agglomerates are present is inferior in light transmittance and thus darker than the portion in which the agglomerates are not present. The case where the aggregate of 30 μm or more was present was judged as ○ (good). The case where the aggregate of 30 μm or more was not present was judged as × (bad).

(adhesion to wafers)

The wafer bonding film was peeled off from the release film, and an adhesive tape (BT-315, manufactured by Nitto Denko Corporation) was bonded to the surface of the wafer bonding film which was in contact with the release film by a hand press roll at room temperature. A slice of 10 mm × 120 mm was cut out from the laminate obtained by lamination with a cutter. The sliced wafer bonded film surface was bonded to a 6 inch wafer using a 2 kg hand roller on a hot plate at 65 °C. After 30 minutes from the completion of the bonding, the peeling adhesion force when the chips were peeled off from the wafer by a width of 10 mm was measured in accordance with JIS Z0237. The peeling angle was 180 degrees and the peeling speed was 300 mm/min. In addition, the tensile tester used AGS-J (trade name) manufactured by Shimadzu Corporation, 50N load cell (model: SM-50N-168, capacity 50N, manufactured by Interface Corporation). When the peeling adhesive force was 1 N/10 mm or more, it was judged as ○ (good), and when it was less than 1 N/10 mm, it was judged as x (bad).

(Measurement of average particle size of filler)

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. The obtained ash was dispersed in pure water, ultrasonically treated for 10 minutes, and the average particle diameter was determined using a laser diffraction scattering type particle size distribution measuring apparatus ("LS 13 320", manufactured by Beckman Coulter, Inc.; wet method). The composition of the wafer bonding film is an organic component other than the filler, and substantially all of the organic components are burned out by the above-described strong heat treatment, and thus the obtained ash is measured as a filler.

(Measurement of thermal conductivity)

The thermal conductivity of the wafer bonded film after thermal curing was measured. The thermal conductivity is obtained by the following equation. The thermal conductivity after heat curing means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

(thermal conductivity) = (thermal diffusion coefficient) × (specific heat) × (specific gravity)

Thermal diffusion coefficient

The wafer bonding film was laminated to a thickness of 1 mm, and then punched into a circular shape having a diameter of 1 cm. Then, it was heated at 130 ° C for 1 hour and then heated at 175 ° C for 5 hours. Using this sample, a thermal expansion coefficient was measured using a laser flash thermal measuring apparatus (manufactured by ULVAC, Inc., TC-9000).

Specific heat

Use DSC (TA instrument system, Q-2000), use according to The predetermined measurement method of JIS-7123 was obtained.

proportion

The electronic scale (made by Shimadzu Corporation, AEL-200) was measured by the Archimedes method.

(Measurement of Melt Viscosity at 130 ° C)

The melt viscosity of the wafer bonded film at 130 ° C before thermal curing was measured. The measurement was performed by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., RS-1). That is, 0.1 g was taken as a sample from the wafer bonding film, and this sample was placed on a plate previously heated to 130 °C. The melt viscosity was set to a value 300 seconds after the start of the measurement. Further, the shear rate was set to 5 sec ^-1 , and the gap between the plates was set to 0.1 mm.

(void evaluation)

The wafer bonded film was attached to a glass wafer having a thickness of 100 μm by thermal lamination using an area of 10 mm × 10 mm to prepare a sample wafer. Next, the sample wafer was bonded to a BGA substrate at a temperature of 130 ° C, 2 kg, and 2 seconds (manufactured by Japan Circuit Industrial Co., Ltd., product name: CA-BGA (2), surface ten-point average roughness (Rz) = 11~13μm). Thereafter, the mixture was heated at 130 ° C for 1 hour under pressure, and then heated at 175 ° C for 5 hours. The pressurization at the time of heat curing was specifically carried out by filling nitrogen gas at 5 kg/cm ² in an oven. Observation was carried out from the glass surface side of the bonded sample wafer using an optical microscope. The binarized software (WinRoof ver. 5.6) was used to calculate the area occupied by the void in the observed image. When the area occupied by the voids was less than 20% with respect to the surface area of the wafer bonding film, it was evaluated as "○", and when it was 20% or more, it was evaluated as "X".

<<Second embodiment of the invention>>

Hereinafter, a suitable embodiment of the second invention will be described in detail by way of examples. Among them, the materials, the blending amount, and the like described in the examples are not particularly In the case of limiting the description, the gist of the second invention is not limited thereto.

The components used in the examples will be described.

Epoxy resin: JER827 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, Mw: 370, liquid at 25 ° C, softening point: less than 25 ° C)

Phenolic resin: MEH-7851-SS manufactured by Minghe Chemical Co., Ltd. (phenolic resin having a biphenyl aralkyl skeleton, hydroxyl equivalent: 203 g/eq., softening point: 67 ° C)

Acrylic rubber: TEISANRESIN SG-P3 manufactured by Nagase ChemteX Corporation (acrylic acid copolymer, Mw: 850,000, glass transition temperature: 12 ° C)

Catalyst: TPP-MK (tetrakis(p-tolylboron) tetraphenylphosphonium) manufactured by Beixing Chemical Industry Co., Ltd.

Filler 1: AO802 manufactured by Admatechs Co., Ltd. (spherical alumina filler, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.95)

Filler 2: ASFP-20 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 0.3 μm, specific surface area: 12.5 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.90)

Filler 3: AO809 manufactured by Admatechs Co., Ltd. (spherical alumina filler, average particle diameter: 10 μm, specific surface area: 1 m ² /g, thermal conductivity: 36 W/m. K)

Filler 4: DAW-07 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 8.1 μm, specific surface area: 0.4 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.91)

Filler 5: DAW-03 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 5.1 μm, specific surface area: 0.5 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.9)

Hydrane coupling agent: KBM-503 (3-methacryloxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd.

The surface treatment method of the filler will be described.

The fillers 1 to 5 were surface-treated with a decane coupling agent to obtain surface-treated fillers 1 to 5. The surface treatment was carried out by a dry method, and the amount of the decane coupling agent shown in the following formula was treated.

Handling amount of decane coupling agent = (weight of filler (g) × specific surface area of filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

[Examples and Comparative Examples] Fabrication of wafer bonding film

According to the compounding ratio described in Table 3, an epoxy resin, a phenol resin, an acrylic rubber, a catalyst, and a surface-treated filler were dissolved and dispersed in methyl ethyl ketone (MEK) to obtain a viscosity-sensitive adhesive composition solution. Thereafter, the adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxyalkylene release treatment. Then, it was dried at 130 ° C for 2 minutes to obtain a wafer bonded film (thickness 25 μm).

[Evaluation]

The obtained wafer bonded film was evaluated as follows. The results are shown in Table 3.

(Measurement of particle size distribution and average particle size of filler)

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. The obtained ash was dispersed in pure water, subjected to ultrasonic treatment for 10 minutes, and a particle size distribution (volume) was determined using a laser diffraction scattering type particle size distribution analyzer ("LS 13 320" manufactured by Beckman Coulter, Inc.; wet method). Benchmark) and average particle size. The composition of the wafer bonding film is an organic component other than the filler, and substantially all of the organic components are burned out by the above-described strong heat treatment, and thus the obtained ash is measured as a filler.

(Measurement of BET specific surface area of filler)

The BET specific surface area was measured by a BET adsorption method (multipoint method). Specifically, the ash obtained by the above-mentioned "measurement of particle size distribution and average particle diameter of the filler" was carried out at 110 ° C using a 4-connected specific surface area/pore distribution measuring apparatus "NOVA-4200e type" manufactured by Quantachrome Corporation. The vacuum was degassed for 6 hours or more, and then measured under nitrogen at a temperature of 77.35 K.

(Measurement of thermal conductivity)

The thermal conductivity of the wafer bonded film after thermal curing was measured. The thermal conductivity is obtained by the following equation. The thermal conductivity after heat curing means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

(thermal conductivity) = (thermal diffusion coefficient) × (specific heat) × (specific gravity)

Thermal diffusion coefficient

The wafer bonding film was laminated to a thickness of 1 mm, and then punched into a circular shape having a diameter of 1 cm. Then, it was heated at 130 ° C for 1 hour and then heated at 175 ° C for 5 hours. Using this sample, a thermal expansion coefficient was measured using a laser flash thermal measuring apparatus (manufactured by ULVAC, Inc., TC-9000).

Specific heat

It was determined by a measurement method according to JIS-7123 using DSC (manufactured by TA Instruments, Q-2000).

proportion

The electronic scale (made by Shimadzu Corporation, AEL-200) was measured by the Archimedes method.

(embedding)

The wafer bonded film was attached to a glass wafer having a thickness of 100 μm by thermal lamination using an area of 10 mm × 10 mm to prepare a sample wafer. Next, the sample wafer was bonded to a BGA substrate at a temperature of 130 ° C, 2 kg, and 2 seconds (manufactured by Japan Circuit Industrial Co., Ltd., product name: CA-BGA (2), surface ten-point average roughness (Rz) = 11~13μm). Thereafter, the mixture was heated at 130 ° C for 1 hour under pressure, and then heated at 175 ° C for 5 hours. The pressurization at the time of heat curing was specifically carried out by filling nitrogen gas at 5 kg/cm ² in an oven. Observation was carried out from the glass surface side of the bonded sample wafer using an optical microscope. The binarized software (WinRoof ver. 5.6) was used to calculate the area occupied by the void in the observed image. When the area occupied by the voids was less than 20% with respect to the surface area of the wafer bonding film, it was evaluated as "○", and when it was 20% or more, it was evaluated as "X".

(reliability (wet reflow resistance))

After attaching the wafer bonding film to a 10 mm square semiconductor wafer under a temperature of 40 ° C, the semiconductor wafer was fixed to the BGA substrate via the wafer bonding film. The fixing conditions were a temperature of 120 ° C, a pressure of 0.1 MPa, and 1 second. Next, the BGA substrate to which the semiconductor wafer was fixed was heat-treated at 130 ° C for 1 hour with a dryer. Thereafter, the package was sealed with a sealing resin (GE-100, manufactured by Nitto Denko Corporation) to obtain a semiconductor package. The packaging conditions were a heating temperature of 175 ° C for 90 seconds. Thereafter, moisture absorption was carried out under conditions of 85 ° C, 60% Rh, and 168 hours, and the semiconductor package was placed in an IR reflow furnace set to be held at 260 ° C or higher for 10 seconds. Thereafter, the semiconductor package was cut with a glass knife, and the cross section was observed with an ultrasonic microscope to confirm the presence or absence of peeling at the boundary between the wafer bonding film and the BGA substrate. When it was confirmed that nine semiconductor wafers were zero, the case where the number of semiconductor wafers which were peeled off was zero was evaluated as ○, and the case of one or more was evaluated as ×.

<<Third embodiment of the invention>>

Hereinafter, a preferred embodiment of the third invention will be exemplarily described in detail. In addition, the material, the amount of preparation, and the like described in the examples are not particularly limited, and the gist of the third invention is not limited thereto.

The components used in the examples will be described.

Epoxy Resin 1: JER827 manufactured by Mitsubishi Chemical Corporation (bisphenol A epoxy resin, Mw: 370, liquid at 25 ° C, softening point: less than 25 ° C)

Epoxy Resin 2: YDF-2001 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (bisphenol F type epoxy resin, softening point: 50~60 °C)

Phenolic resin: MEH-7851-SS manufactured by Minghe Chemical Co., Ltd. (phenolic resin having a biphenyl aralkyl skeleton, hydroxyl equivalent: 203 g/eq., softening point: 67 ° C)

Acrylic rubber: TEISANRESIN SG-70L manufactured by Nagase ChemteX Corporation (acrylic acid copolymer, Mw: 900,000, glass transition temperature: -13 ° C)

Catalyst: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

Filler 1: DAW-05 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 5 μm, specific surface area: 0.4 m ² /g, thermal conductivity: 36 W/m.K, sphericity: 0.91)

Filler 2: AO802 manufactured by Admatechs Co., Ltd. (spherical alumina filler, average particle diameter: 0.6 μm, thermal conductivity: 36 W/m.K, sphericity: 0.95)

矽Case coupling agent: KBM- manufactured by Shin-Etsu Chemical Industry Co., Ltd. 503 (3-methacryloxypropyltrimethoxydecane)

The surface treatment method of the filler will be described.

The fillers 1 to 2 were surface-treated with a decane coupling agent to obtain surface-treated fillers 1 to 2. The surface treatment was carried out by a dry method and treated with a decane coupling agent in an amount shown by the following formula.

Handling amount of decane coupling agent = (weight of filler (g) × specific surface area of filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

[Examples and Comparative Examples] Fabrication of wafer bonding film

According to the compounding ratio described in Table 4, an epoxy resin, a phenol resin, an acrylic rubber, a catalyst, and a surface-treated filler were dissolved and dispersed in methyl ethyl ketone (MEK) to obtain a viscosity-adhesive agent composition solution suitable for coating. Thereafter, the adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxyalkylene release treatment. Then, it was dried at 130 ° C for 2 minutes to obtain a wafer bonded film (thickness 25 μm).

[Evaluation]

The obtained wafer bonded film was evaluated as follows. The results are shown in Table 4.

(Measurement of linear expansion coefficient)

After laminating the wafer bonding film to form a laminate having a thickness of 1000 μm, the laminate was die-cut into 4 mm. (diameter). Will be 4mm The laminate was heated at 130 ° C for 1 hour, and then heated at 175 ° C for 5 hours to be solidified to obtain a measurement sample. After the measurement sample was attached to the measurement jig of the thermomechanical analysis device (TMA8310 manufactured by Rigaku Corporation), the injection load was 0.003 N and the probe diameter was 3 mm in the temperature range of -50 ° C to 300 ° C. The expansion ratio was measured under the conditions of a temperature increase rate of 5 ° C /min. The coefficient of linear expansion (CTEα1) below the glass transition temperature was calculated from the expansion ratio at 50 ° C to 70 ° C, and the coefficient of linear expansion (CTE α 2 ) at a temperature exceeding the glass transition temperature was calculated from the expansion ratio at 140 ° C to 180 ° C. .

(Measurement of glass transition temperature and measurement of storage modulus at 260 ° C)

The wafer bonded film was laminated to form a laminate having a thickness of 1000 μm. The laminate was heated at 130 ° C for 1 hour, and then heated at 175 ° C for 5 hours to be solidified, and then a measurement sample having a length of 10 mm × a width of 30 mm was cut out from the cured product. For the measurement sample, a storage modulus and a loss modulus at -50 ° C to 300 ° C were measured using a solid viscoelasticity measuring apparatus (RSAII, manufactured by Rheometric Scientific, Inc.). The measurement conditions were a frequency of 1 Hz and a temperature increase rate of 10 ° C/min. Further, the glass transition temperature was obtained by calculating the value of tan δ (E" (loss modulus) / E' (storage modulus).

(reliability (wet reflow resistance))

Attach the wafer bonding film to 5mm four at a temperature of 40 ° C After the square semiconductor wafer, the semiconductor wafer is bonded to the lead frame (MF-202) via the wafer bonding film. The joining conditions were a temperature of 120 ° C, a pressure of 0.1 MPa, and 1 second. Next, the lead frame to which the semiconductor wafer was bonded was heat-treated at 130 ° C for 1 hour in a nitrogen atmosphere. Then, it was packaged by a sealing resin (GE-7470L-Q, manufactured by Hitachi Chemical Co., Ltd.) to obtain a semiconductor package. The packaging conditions were a heating temperature of 175 ° C for 90 seconds. Thereafter, moisture absorption was carried out under conditions of 85 ° C, 60% Rh, and 168 hours, and the semiconductor package was placed in an IR reflow furnace set to be held at 260 ° C or higher for 10 seconds. Thereafter, the semiconductor package was cut with a glass knife, and the cross section was observed with an ultrasonic microscope to confirm the presence or absence of peeling at the boundary between the wafer bonding film and the lead frame. When eight semiconductor wafers were confirmed, the case where the number of semiconductor wafers which were peeled off was zero was evaluated as ○, and the case of one or more was evaluated as ×.

(Measurement of average particle size of filler)

The wafer-bonding film was placed in a crucible, and ashed by heating at 700 ° C for 2 hours in an air atmosphere. The obtained ash was dispersed in pure water, and subjected to ultrasonic treatment for 10 minutes, and the average particle diameter was determined by a laser diffraction scattering type particle size distribution measuring apparatus ("LS 13 320", manufactured by Beckman Coulter, Inc.; wet method). The composition of the wafer bonding film is an organic component other than the filler, and substantially all of the organic components are burned out by the above-described strong heat treatment, and thus the obtained ash is measured as a filler.

<<Fourth embodiment of the invention>>

Hereinafter, a suitable embodiment of the fourth invention will be exemplarily described in detail. In addition, the material, the amount of preparation, and the like described in the examples are not particularly limited, and the gist of the fourth invention is not limited thereto. "Parts" means "parts by weight".

(Example 1) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (e) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 150 mPa at room temperature. s, get the adhesive composition dissolved liquid.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A type epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 8.6 parts

(b) Phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Megumi Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 10.6 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-70L) 1 part

(d) Curing-promoting catalyst (manufactured by Shikoku Chemicals Co., Ltd., product name: 2PHZ-PW, 2-phenyl-4,5-dihydroxymethylimidazole) 0.2 parts

(e) Spherical alumina filler A: DAW-03 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 3 μm, specific surface area: 0.4 m ² /g, thermal conductivity: 36 W/m.K 80 copies

The spherical alumina filler A was previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

Applying the solution of the adhesive composition to the demolding of the polyoxyalkylene A coating film was formed on a release-treated film (first separator) made of a polyethylene terephthalate film having a thickness of 50 μm, and then dried at a drying temperature of 130 ° C for 2 minutes. Thereafter, a release-treated film (second separator) composed of a polyethylene terephthalate film having a thickness of 50 μm, which was subjected to polyoxane release treatment, was superposed, at a temperature of 65 ° C and a pressure of 0.4. The coating film was sandwiched between the first separator and the second separator at a rate of 10 m/min under the condition of Pa and held. Thus, a wafer bonding film A having a thickness of 30 μm was produced.

(Example 2) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (e) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 150 mPa at room temperature. s, a solution of the binder composition is obtained.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 7.3 parts

(b) Phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Megumi Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 8.9 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-70L) 4 parts

(d) Curing-promoting catalyst (manufactured by Shikoku Chemicals Co., Ltd., product name: 2PHZ-PW, 2-phenyl-4,5-dihydroxymethylimidazole) 0.2 parts

(e) Spherical alumina filler A: DAW-03 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 3 μm, specific surface area: 0.4 m ² /g, thermal conductivity: 36 W/m.K 80 copies

The spherical alumina filler A was previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

The adhesive composition solution is formed on a release-treated film (first separator) composed of a polyethylene terephthalate film having a thickness of 50 μm which is subjected to polyoxane release treatment. After coating the film, it was dried at a drying temperature of 130 ° C for 2 minutes. Thereafter, a release-treated film (second separator) composed of a polyethylene terephthalate film having a thickness of 50 μm, which was subjected to polyoxane release treatment, was superposed, at a temperature of 65 ° C and a pressure of 0.4. The coating film was sandwiched between the first separator and the second separator at a rate of 10 m/min under the condition of Pa and held. Thus, a wafer bonding film B having a thickness of 30 μm was produced.

(Comparative Example 1) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (e) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 150 mPa at room temperature. s, the adhesive combination is obtained and the solution is used.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 6.4 parts

(b) Phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Megumi Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 7.8 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-70L) 6.0 parts

(d) Curing-promoting catalyst (manufactured by Shikoku Chemicals Co., Ltd., product name: 2PHZ-PW, 2-phenyl-4,5-dihydroxymethylimidazole) 0.2 parts

(e) Spherical alumina filler C (ASFP-20 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 0.3 μm, specific surface area: 12.5 m ² /g, thermal conductivity: 36 W/m. K)) 80 copies

The spherical alumina filler C was previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

The adhesive composition solution is formed on a release-treated film (first separator) composed of a polyethylene terephthalate film having a thickness of 50 μm which is subjected to polyoxane release treatment. After coating the film, it was dried at a drying temperature of 130 ° C for 2 minutes. Thereafter, a release-treated film (second separator) composed of a polyethylene terephthalate film having a thickness of 50 μm, which was subjected to polyoxane release treatment, was superposed, at a temperature of 65 ° C and a pressure of 0.4. The coating film was sandwiched between the first separator and the second separator at a rate of 10 m/min under the condition of Pa and held. Thus, a wafer bonding film C having a thickness of 30 μm was produced.

(Comparative Example 2) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (e) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 150 mPa at room temperature. s, the adhesive combination is obtained and the solution is used.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A type epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 8.6 parts

(b) Phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Megumi Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 10.6 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-70L) 1 part

(d) Curing-promoting catalyst (manufactured by Shikoku Chemicals Co., Ltd., product name: 2PHZ-PW, 2-phenyl-4,5-dihydroxymethylimidazole) 0.2 parts

(e) Spherical alumina filler B: DAW-03 manufactured by Electrochemical Industry Co., Ltd. (spherical alumina filler, average particle diameter: 3 μm, specific surface area: 0.4 m ² /g, thermal conductivity: 36 W/m.K , no surface treatment) 80 parts

The adhesive composition solution is formed on a release-treated film (first separator) composed of a polyethylene terephthalate film having a thickness of 50 μm which is subjected to polyoxane release treatment. After coating the film, it was dried at a drying temperature of 130 ° C for 2 minutes. Thereafter, a release-treated film (second separator) composed of a polyethylene terephthalate film having a thickness of 50 μm, which was subjected to polyoxane release treatment, was superposed, at a temperature of 65 ° C and a pressure of 0.4. The coating film was sandwiched between the first separator and the second separator at a rate of 10 m/min under the condition of Pa and held. Thus, a wafer bonding film D having a thickness of 30 μm was produced.

The average particle diameter of the entire filler in the wafer bonded film of the examples and the comparative examples and the specific surface area of the entire filler were as shown in Table 5. In addition, the filling amount of the filler with respect to the entire wafer bonding film, the ratio of the thermosetting resin in the resin component (in the total amount of the thermosetting resin to the thermoplastic resin), and the thermoplastic resin in the resin component (in the total amount of the thermosetting resin and the thermoplastic resin) The ratio is also shown in Table 5.

(Measurement of Melt Viscosity at 80 ° C)

The melt viscosity of the wafer bonding films A to D at 80 ° C before thermal curing was measured. The measurement was performed by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., RS-1). That is, 0.1 g was taken as a sample from each of the wafer bonding films A to D, and the sample was placed on a plate previously heated to 80 °C. The melt viscosity was set to a value 300 seconds after the start of the measurement. Further, the shear rate was set to 5 sec ^-1 , and the gap between the plates was set to 0.1 mm. The results are shown in Table 5 below.

(Measurement of thermal conductivity)

The thermal conductivity of the wafer bonded films A to D was measured after thermal curing. The thermal conductivity is obtained by the following equation. The results are shown in Table 5. The thermal conductivity after heat curing means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

(thermal conductivity) = (thermal diffusion coefficient) × (specific heat) × (specific gravity)

<thermal diffusion coefficient>

The wafer bonding film was laminated to a thickness of 1 mm, and then punched into a shape of 1 cm Φ. Then, it was heated at 130 ° C for 1 hour and then heated at 175 ° C for 5 hours. Using this sample, a thermal expansion coefficient was measured using a laser flash thermal measuring apparatus (manufactured by ULVAC, Inc., TC-9000).

<specific heat>

It was determined by a measurement method according to JIS-7123 using DSC (manufactured by TA Instruments, Q-2000).

<specific gravity>

The electronic scale (manufactured by Shimadzu Corporation, AEL-200) was used and measured by the Archimedes method.

(Measurement of surface roughness Ra)

The wafer bonding films A to D were bonded to a smooth mirror wafer and fixed, and the surface roughness Ra was measured using a surface roughness measuring machine (manufactured by MITUTOYO CO., LTD., product name "SURFTEST. SJ-301"). The results are shown in Table 5.

(Evaluation of water intrusion during cutting)

The wafer bonding film A to D was bonded to a dicing tape (P-2130, manufactured by Nitto Denko Corporation) at 40 ° C using a laminator, and further bonded at 65 ° C, 0.1 MPa, and 10 mm / sec on the adhesive film. 50 μm 8-inch wafer. Thereafter, it was bonded to an 8-inch cutting ring (DTF2-8-1, manufactured by DISCO Corporation) for cutting. A cutting device (DFD6361, manufactured by DISCO Corporation) was used, NBC-ZH203O-SE27HEDD (manufactured by DISCO Corporation) was used for the Z1 cutting blade, and NBC-ZH203O-SE27HEFF (manufactured by DISCO Corporation) was used for the Z2 blade. Regarding the blade height, Z1 is set to a height half cut in the wafer, and Z2 is set to a height of 20 μm cut in the dicing tape. The cutting blade was rotated at a speed of 40,000 rpm, a cutting speed of 30 mm/sec, and a water volume of 1 L/min, and was performed in a step cut manner. Regarding the intrusion of water, the cut sample was observed from the side of the dicing tape to confirm whether water entered between the wafer bonding film and the dicing tape, in the case of water immersion or wafer bonding. When peeling occurred between the film and the dicing tape, it was judged that water invaded. Each of the examples was cut into 10 pieces, and even if one piece of water invaded, it was evaluated as "x", and no water intrusion was evaluated as "○". The results are shown in Table 5.

<<Fifth embodiment of the invention>>

Hereinafter, a preferred embodiment of the fifth invention will be exemplarily described in detail. In addition, the material, the amount of preparation, and the like described in the examples are not specifically limited, and the gist of the fifth invention is not limited thereto. "Parts" means "parts by weight".

(Example 1) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (f) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 100 mPa at room temperature. s, a solution of the binder composition is obtained.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 9.5 parts

(b) phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Minghe Chemical Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 9.5 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-P3, weight average molecular weight: 850,000, glass transition temperature: 12 ° C) 1 part

(d) Curing-promoting catalyst (manufactured by Kitai Chemical Co., Ltd., product name: TPP-MK, tetrakis(p-tolylborate) tetraphenylphosphonium) 0.2 parts

(e) Spherical alumina filler A (manufactured by Electric Chemical Industry Co., Ltd., product name: DAW-05, average particle diameter: 5.1 μm, specific surface area: 0.5 m ² /g) 60 parts

(f) Spherical alumina filler B (manufactured by Admatechs Co., Ltd., product name: AO802, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g) 20 parts

The spherical alumina filler A and the spherical alumina filler B were previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

Applying the solution of the adhesive composition to a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxane release treatment, and then Dry at 130 ° C for 2 minutes. Thus, a wafer bonding film A having a thickness of 25 μm was produced.

(Example 2) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (f) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 100 mPa at room temperature. s, a solution of the binder composition is obtained.

(a) Epoxy resin (Mitsubishi Chemical Co., Ltd., product name: JER827 (bisphenol A type epoxy resin), liquid at room temperature (softening point below 25 ° C)) 6.5 parts

(b) phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Megumi Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g / eq.) 7 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-P3, weight average molecular weight: 850,000, glass transition temperature: 12 ° C) 1.5 parts

(d) Curing-promoting catalyst (manufactured by Kitai Chemical Co., Ltd., product name: TPP-MK, tetrakis(p-tolylboron) tetraphenylphosphonium) 0.15 parts

(e) Spherical alumina filler A (manufactured by Electric Chemical Industry Co., Ltd., product name: DAW-05, average particle diameter: 5.1 μm, specific surface area: 0.5 m ² /g) 60 parts

(f) Spherical aluminum-like alumina filler B (manufactured by Admatechs Co., Ltd., product name: AO802, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g) 25 parts

The spherical alumina filler A and the spherical alumina filler B were previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

The adhesive is combined and applied to a release-treated film (release liner) made of a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to polyoxyalkylene release treatment. It was then dried at 130 ° C for 2 minutes. Thus, a wafer bonding film B having a thickness of 25 μm was produced.

(Example 3) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (f) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 100 mPa at room temperature. s, a solution of the binder composition is obtained.

(a) Epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: JER827 (bisphenol A epoxy resin), liquid at room temperature (softening point is 25 ° C or less)) 4.2 parts

(b) phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Minwa Kasei Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g/eq.) 4.3 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-P3, weight average molecular weight: 850,000, glass transition temperature: 12 ° C) 1.5 parts

(d) Curing-promoting catalyst (manufactured by Kitai Chemical Co., Ltd., product name: TPP-MK, tetrakis(p-tolylboron) tetraphenylphosphonium) 0.15 parts

(e) Spherical alumina filler A (manufactured by Electric Chemical Industry Co., Ltd., product name: DAW-05, average particle diameter: 5.1 μm, specific surface area: 0.5 m ² /g) 68 parts

(f) Spherical alumina filler B (manufactured by Admatechs Co., Ltd., product name: AO802, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g) 22 parts

The spherical alumina filler A and the spherical alumina filler B were previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

Applying the solution of the adhesive composition to a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm subjected to polyoxane release treatment, and then Dry at 130 ° C for 2 minutes. Thus, a wafer bonding film C having a thickness of 25 μm was produced.

(Comparative Example 1) <Production of Thermosetting Wafer Bonding Film>

The following (a) to (e) were dissolved in MEK (methyl ethyl ketone), and the concentration was adjusted so that the viscosity was 100 mPa at room temperature. s, the adhesive combination is obtained and the solution is used.

(a) Epoxy resin (Mitsubishi Chemical Co., Ltd., product name: JER827 (bisphenol A type epoxy resin), liquid at room temperature (softening point below 25 ° C) 8 parts

(b) phenolic resin (phenolic resin having a biphenyl aralkyl skeleton, manufactured by Minghe Chemical Co., Ltd., product name: MEH-7851SS, softening point 67 ° C, hydroxyl equivalent 203 g / eq.) 8 parts

(c) Acrylic copolymer (manufactured by Nagase ChemteX Corporation, product name: TEISANRESIN SG-P3, weight average molecular weight: 850,000, glass transition temperature: 12 ° C) 4 parts

(d) Curing-promoting catalyst (manufactured by Kitai Chemical Co., Ltd., product name: TPP-MK, tetrakis(p-tolylborate) tetraphenylphosphonium) 0.2 parts

(e) Spherical alumina filler B (manufactured by Admatechs Co., Ltd., product name: AO802, average particle diameter: 0.7 μm, specific surface area: 7.5 m ² /g) 80 parts

The spherical alumina filler A and the spherical alumina filler B were previously subjected to surface treatment. The surface treatment was carried out by a dry method, and treatment was carried out using a decane coupling agent in an amount shown by the following formula (a treatment amount of a decane coupling agent). The decane coupling agent used KBM503 of Shin-Etsu Chemical Co., Ltd.

(Handling amount of decane coupling agent) = (weight of alumina filler (g) × specific surface area of alumina filler (m ² /g)) / minimum coverage area of decane coupling agent (m ² /g)

Minimum coverage area of decane coupling agent (m ^{2 /} g) = 6.02 × 10 ²³ × 13 × 10 ^-20 / molecular weight of decane coupling agent

The adhesive is combined and coated with a solution of polyethylene terephthalate film having a thickness of 50 μm which has been subjected to polyoxane release treatment. The release film (release liner) was formed and then dried at 130 ° C for 2 minutes. Thus, a wafer bonding film D having a thickness of 25 μm was produced.

The average particle diameter of the entire filler (spherical alumina filler A and spherical alumina filler B) in the wafer bonded film of the examples and the comparative examples and the specific surface area of the entire filler are shown in Table 6. In addition, the filling amount of the filler with respect to the entire wafer bonding film, the ratio of the thermosetting resin in the resin component (in the total amount of the thermosetting resin to the thermoplastic resin), and the thermoplastic resin in the resin component (in the total amount of the thermosetting resin and the thermoplastic resin) The ratios are also shown in Table 6.

(Measurement of Melt Viscosity at 80 ° C)

The melt viscosity of the wafer bonding films A to D at 80 ° C before thermal curing was measured. The measurement was performed by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., RS-1). That is, 0.1 g was taken as a sample from each of the wafer bonding films A to D, and the sample was fed to a plate previously heated to 80 °C. The melt viscosity was set to a value 300 seconds after the start of the measurement. Further, the shear rate was set to 5 sec ^-1 , and the gap between the plates was set to 0.1 mm. The results are shown in Table 6 below.

(Measurement of thermal conductivity)

The thermal conductivity of the wafer bonded films A to C was measured after thermal curing. The thermal conductivity is obtained by the following equation. The results are shown in Table 6. The thermal conductivity after heat curing means a thermal conductivity after heating at 130 ° C for 1 hour and then heating at 175 ° C for 5 hours.

(thermal conductivity) = (thermal diffusion coefficient) × (specific heat) × (specific gravity)

<thermal diffusion coefficient>

The wafer bonding film was laminated to a thickness of 1 mm, and then punched into a shape of 1 cm Φ. Then, it was heated at 130 ° C for 1 hour and then heated at 175 ° C for 5 hours. Using this sample, a thermal expansion coefficient was measured using a laser flash thermal measuring apparatus (manufactured by ULVAC, Inc., TC-9000).

<specific heat>

It was determined by a measurement method according to JIS-7123 using DSC (manufactured by TA Instruments, Q-2000).

<specific gravity>

The electronic scale (manufactured by Shimadzu Corporation, AEL-200) was used and measured by the Archimedes method.

(fixed evaluation)

The fixation evaluation was carried out using a product obtained by laminating a wafer bonding film on a dicing sheet.

<Creation of cutting tape adhesive>

4 parts of 2-ethylhexyl acrylate, 3 parts of butyl acrylate, 100 parts of 2-hydroxyethyl acrylate, and benzoic acid peroxide were placed in a reaction vessel equipped with a condenser, a nitrogen gas introduction tube, a thermometer, and a stirring device.醯0.2 copies to Further, 20 parts of acetic acid was subjected to a polymerization treatment at 61 ° C for 6 hours in a nitrogen gas stream to obtain an acrylic polymer A. The acrylic polymer A had a weight average molecular weight Mw of 300,000, a glass transition temperature (Tg) of -16 ° C, an iodine value of 2, and a hydroxyl value (mgKOH/g) of 30.

To the obtained acrylic polymer A, 24.1 parts of 2-methylpropenyloxyethyl isocyanate (hereinafter also referred to as "MOI", manufactured by Showa Denko Co., Ltd.) was added, and the mixture was heated at 50 ° C for 48 hours in an air stream. The reaction treatment was carried out to obtain an acrylic polymer A'. Next, 3 parts of a polyisocyanate compound (trade name "CORONATE L", manufactured by Nippon Polyurethane Co., Ltd.) and a photopolymerization initiator (trade name "IRGACURE 651" were added to 100 parts of the acrylic polymer A'. 3 parts of Ciba Specialty Chemicals Inc. was dissolved in toluene to obtain a binder composition solution having a concentration of 20% by weight. The substrate was prepared by using a polyethylene terephthalate film (PET film) having a thickness of 50 μm, and the obtained adhesive composition solution was applied thereon and dried to form a binder layer having a thickness of 30 μm. This gives a cut film.

The dicing film and the wafer bonding film were bonded at room temperature, 0.15 MPa, and 10 mm/sec, thereby producing a wafer bonding film with a dicing sheet.

The fixing evaluation was carried out using a wafer bonding apparatus (MA-3000II) manufactured by Nitto Seiki Co., Ltd. Specifically, the wafer-bonded film of the dicing sheet obtained above was bonded to a 12-inch wafer polished to 50 μm. The bonding conditions were a bonding speed of 15 mm/sec, a bonding temperature of 80 ° C, and a bonding pressure of 0.15 MPa.

The case where the film can be satisfactorily fixed is evaluated as "○", and the wafer is cracked, the bonded portion of the wafer bonding film and the wafer is trapped in the bubble, and the wafer bonding film and the wafer are poorly bonded. The case where color unevenness (partially cloudy state, etc.) occurred was evaluated as "x". The results are shown in Table 6.

1‧‧‧Substrate

2‧‧‧Binder layer

2a‧‧‧corresponding to part 39

Other parts of 2b‧‧‧2a

3‧‧‧ wafer bonding film (thermosetting wafer bonding film)

3a‧‧‧Working part attachment

Parts other than 3b‧‧3a

4‧‧‧Semiconductor wafer

10‧‧‧ wafer bonding film with dicing sheets

11‧‧‧Cut slices

Claims (10)

A thermosetting wafer-bonding film comprising thermally conductive particles, wherein the thermally conductive particles are surface-treated with a decane coupling agent, and the content of the thermally conductive particles is 75% by weight or more based on the total amount of the thermosetting wafer-bonding film. The thermal conductivity after heat curing is 1W/m. K or more. The thermosetting wafer bonding film according to claim 1, wherein the thermal conductivity of the thermally conductive particles is 12 W/m. K or more. The thermosetting wafer-bonding film according to claim 1 or 2, wherein the decane coupling agent contains a hydrolyzable group, and the hydrolyzable group is a methoxy group and/or an ethoxy group. The thermosetting die-bonding film according to claim 1, wherein the decane coupling agent comprises an organic functional group, and the organic functional group comprises an acryloyl group, a methacryl fluorenyl group, an epoxy group, or a phenylamino group. At least one of the groups. The thermosetting wafer bonding film according to claim 1, wherein the aforementioned decane coupling agent does not contain a primary amino group, a mercapto group, and an isocyanate group. The thermosetting die-bonding film according to claim 1, which has a melt viscosity of 300 Pa at 130 ° C. s below. The thermosetting wafer bonding film according to claim 1, which has a thickness of 50 μm or less. A method of manufacturing a semiconductor device, comprising the steps of: preparing the thermosetting wafer bonding film according to any one of claims 1 to 7; The step of bonding the semiconductor wafer wafer to the adherend via the aforementioned thermosetting wafer bonding film. A die-bonding film with a dicing sheet, wherein the dicing sheet has a thermosetting wafer bonding film according to any one of claims 1 to 7, wherein the dicing sheet has an adhesive layer laminated on the substrate. A method of manufacturing a semiconductor device, comprising the steps of: preparing a wafer bonding film with a dicing sheet according to claim 9; and forming the aforementioned thermosetting wafer bonding film and semiconductor wafer of the wafer bonding film with the dicing sheet a step of bonding the back surface; cutting the semiconductor wafer together with the thermosetting wafer bonding film to form a wafer-shaped semiconductor wafer; and attaching the semiconductor wafer together with the thermosetting wafer bonding film a step of picking up the wafer-bonding film of the dicing sheet; and bonding the aforementioned semiconductor wafer wafer to the adherend via the aforementioned thermosetting wafer bonding film.