KR100776313B1 - Adhesive sheet for producing semiconductor device, semiconductor device, and production method for semiconductor device - Google Patents

Abstract

An adhesive sheet for manufacturing a semiconductor device which is adhered to a lead frame or a wiring board of a semiconductor device so as to be peeled off, the adhesive sheet comprising a base material and an adhesive layer, wherein the adhesive layer comprises a thermosetting resin component (a), a thermoplastic resin component (b), An adhesive sheet for producing a semiconductor device containing a fluorine-based additive (c) is provided. This suppresses the generation of outgas components generated when using a silicone pressure sensitive adhesive and the like, while maintaining the wire bonding properties and mold flash characteristics of the thermosetting adhesive when used in the manufacture of semiconductor devices such as QFN. It is possible to prevent the defective product of the semiconductor device.

Adhesive, adhesive sheet for semiconductor device manufacturing, adhesive layer, adhesion trace, lead frame, wiring board

Description

Adhesive sheet for semiconductor device manufacturing, semiconductor device, and manufacturing method thereof {ADHESIVE SHEET FOR PRODUCING SEMICONDUCTOR DEVICE, SEMICONDUCTOR DEVICE, AND PRODUCTION METHOD FOR SEMICONDUCTOR DEVICE}

1 is a schematic plan view showing an example of a very preferable lead frame used when manufacturing a QFN using the adhesive sheet for semiconductor device manufacture of the present invention.

FIG. 2 is a sectional view taken along the line AA ′ of FIG. 1, showing an example of a manufacturing process of QFN. FIG.

<Description of the symbols for the main parts of the drawings>

10: Adhesive sheet for semiconductor device manufacturing

20: lead frame

30: Semiconductor element

31: Bonding wire

40: bag resin

The present invention relates to an adhesive sheet for manufacturing a semiconductor device, a semiconductor device, and a manufacturing method thereof.

This application claims priority based on Japanese Patent Application No. 2005-09481, filed March 30, 2005, Japanese Patent Application No. 2005-316560 and Japanese Patent Application No. 2005-316561, filed on October 31, 2005. To apply to.

In recent years, with the miniaturization and multifunctionalization of electronic devices such as portable PCs and mobile phones, in addition to miniaturization and high integration of electronic parts constituting electronic devices, high-density packaging technology of electronic parts has been required. Under these circumstances, surface-mounted semiconductor devices such as Chip Scale Pakeage (CSP) capable of high-density mounting instead of peripheral-mounted semiconductor devices such as conventional quad flat packages (QFPs) and small outline packages (SOPs) are noted. Is getting. Among the CSPs, quad flat non-leaded (QFN) is particularly preferable because it can be manufactured by applying a conventional semiconductor device manufacturing technique, and is mainly used as a small terminal type semiconductor device of 100 pins or less.

The following method is known as a manufacturing method of QFN.

First, an adhesive sheet is adhered to one side of the lead frame (adhesion step of the adhesive sheet), and semiconductor elements such as IC chips are mounted on the semiconductor element mounting portions (die pad portions) formed in a plurality of lead frames, respectively. (Die attach process). Next, a plurality of leads and semiconductor elements disposed along the outer circumference of each semiconductor element mounting portion of the lead frame are electrically connected by the bonding wires (wire bonding step). Next, the semiconductor element mounted on the lead frame is sealed with a sealing resin (resin sealing step). By peeling an adhesive sheet from a lead frame (adhesive sheet peeling process), the QFN unit by which several QFN was arranged can be formed. Finally, by dicing this QFN unit along the outer periphery of each QFN (dicing process), several QFN can be manufactured simultaneously.

In Japanese Patent Laid-Open Nos. 2002-184801 and 2000-294579, an adhesive sheet using a silicone pressure sensitive adhesive or an acrylic pressure sensitive adhesive is used as a method for producing QFN. However, in the case of using a silicone pressure sensitive adhesive or an acrylic pressure sensitive adhesive, mold flash due to the pressure sensitive adhesive may occur. Moreover, the outgas component may generate | occur | produce from the adhesive of an adhesive sheet by heating. This outgas component may adhere to the lead frame surface and cause bonding failure of the bonding wire. In addition, the adhesion between the lead frame and the encapsulating resin may sometimes be caused. Thereby, there exists a possibility that the yield in semiconductor device manufacture may fall, and reliability may fall.

By the way, for the purpose of improving such a problem, Unexamined-Japanese-Patent No. 2003-336015 has proposed the adhesive tape which applied the thermosetting adhesive agent.

It is common to further improve wire bonding characteristics by performing plasma cleaning prior to the wire bonding step to remove impurities adhering to the surface.

However, when using the conventional adhesive sheet for semiconductor device manufacturing using the thermosetting adhesive, when the exposed surface surface layer of the adhesive sheet becomes rough by plasma cleaning and peels off the adhesive sheet for semiconductor, it is connected to the connection terminal of the semiconductor device and the encapsulating resin surface. Adhesive transfer (hereinafter referred to as "adherence traces") may occur. If such adhesion traces occur, an adhesive may adhere to a portion encapsulated with a sealing resin or an external connection terminal of a lead located in the vicinity thereof, resulting in poor connection to the manufactured semiconductor device.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has a thermosetting adhesive that is used in the production of semiconductor devices such as QFN while suppressing the generation of outgas components generated by using a silicone adhesive or the like. It is an object of the present invention to provide an adhesive sheet for manufacturing a semiconductor device, a semiconductor device, and a method of manufacturing the same, which can prevent adhesion traces while maintaining excellent wire bonding properties and mold flash characteristics. It is done.

In addition, an object of the present invention is to provide an adhesive sheet for semiconductor device manufacturing that can obtain a semiconductor device having good wire bonding characteristics, excellent adhesion between a lead frame and an encapsulating resin, and excellent reliability without performing plasma cleaning prior to the wire bonding process. .

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides an adhesive sheet for manufacturing a semiconductor device which is adhered to a lead frame or a wiring board of a semiconductor device so as to be peeled off, the adhesive sheet comprising a substrate and an adhesive layer, wherein the adhesive layer comprises a thermosetting resin component (a). ), A thermoplastic resin component (b) and a fluorine-based additive (c).

In the adhesive sheet for the first semiconductor device, the fluorine-based additive (c) is preferably one or more selected from the group consisting of fluorine-containing grafted polymers, fluorine-containing block copolymers and fluorine-containing aliphatic polymer esters.

In addition, in order to achieve the above object, the present invention provides an adhesive sheet for manufacturing a semiconductor device which is adhered to a lead frame or wiring board of a semiconductor device so as to be peeled off, the adhesive sheet comprising a base material and an adhesive layer, wherein the adhesive layer is a fluorine resin. An adhesive sheet for manufacturing a second semiconductor device is provided.

In the adhesive sheet for the second semiconductor device, the adhesive layer contains a thermosetting resin component (a1) and a thermoplastic resin component (b1), and either of the thermosetting resin component (a1) and the thermoplastic resin component (b1) It is preferable that it is olefin resin containing fluorine.

It is also preferable that mass ratio (a1) / (b1) of the thermosetting resin component (a1) and the thermoplastic resin component (b1) of the said adhesive bond layer is 0.05-0.43.

It is also preferable that the mass mean molecular weight of the thermoplastic resin component (b1) is 2,000 to 1,000,000.

It is also preferable that the storage modulus after hardening of the said adhesive bond layer is 0.1 Mpa or more at 150-250 degreeC.

It is also preferable that the adhesive strength in 150-200 degreeC of the adhesive bond layer after hardening is 0.03-5 N / cm.

Moreover, it is also preferable that the said base material is a heat resistant film with a glass transition temperature of 150 degreeC or more and a thermal expansion coefficient of 5-50 ppm / degreeC.

It is also preferable that the base material is a metal foil having a thermal expansion coefficient of 5 to 50 ppm / ° C.

In addition, the present invention, in order to achieve the above object, in the adhesive sheet for manufacturing a semiconductor device which is adhered to the lead frame or wiring board of the semiconductor device so as to be peeled off, provided with a substrate and an adhesive layer, the adhesive layer is a fluororesin and reactive Provided is an adhesive sheet for manufacturing a third semiconductor device, characterized by containing an elastomer.

In the adhesive sheet for manufacturing the third semiconductor device, the fluororesin is a copolymer formed by polymerizing a monomer raw material containing fluoroolefin and vinyl ether and / or a copolymer formed by polymerizing monomer raw material including fluoroolefin and vinyl ester. desirable.

It is also preferable that the reactive elastomer is a maleic anhydride-containing styrene-ethylene-butylene copolymer.

In the adhesive sheets for manufacturing the first to third semiconductor devices, it is preferable that a protective film is provided on one side of the adhesive layer.

delete

In addition, the present invention, in order to achieve the above object, in manufacturing a semiconductor device using the adhesive sheet for manufacturing the first to third semiconductor device, the semiconductor device manufacturing method is the adhesive for manufacturing the semiconductor device on one side of the lead frame Affixing a sheet is provided. The semiconductor device is mounted on a predetermined region of the other side of the lead frame. A bonding wire is formed to electrically connect the semiconductor device and a portion of the lead frame around the semiconductor device. An encapsulation resin is formed to cover the semiconductor device and the bonding wire. The adhesive sheet for manufacturing a semiconductor device is peeled from the lead frame.

In addition, the "fluoroolefin" in this specification and a claim is taken as the concept including what one part or all part of the hydrogen atom of an olefin is substituted by the fluorine atom. For example, a compound in which part or all of hydrogen atoms of an olefin are substituted with fluorine atoms, and a compound in which hydrogen atoms of olefins are substituted with fluorine atoms and a part or all of remaining hydrogen atoms are substituted with other atoms such as chlorine atoms It is a concept to say.

In addition, "fluorine resin" means resin containing a fluorine atom widely.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The adhesive sheet of the present invention is adhered to the lead frame or the wiring board of the semiconductor device so as to be peeled off. Here, the lead frame is a conductive pattern formed by etching or pressing a metal plate, and the wiring board is formed of a conductive material on the surface of the electrically insulating substrate (or may include an inner surface). It is fixed.

In addition, in the following description, although the lead frame is demonstrated as a sticking object for convenience, it is the same also about a wiring board.

The adhesive sheet of this invention has a base material and an adhesive bond layer.

As a base material, what has heat resistance, for example, a heat resistant resin film, metal foil, etc. are mentioned.

When manufacturing a semiconductor device such as QFN using the adhesive sheet of the present invention, the adhesive sheet is exposed to a die at high temperature, but when a heat resistant resin film is used as the substrate, the coefficient of thermal expansion of the heat resistant film is determined by the glass transition temperature ( Tg) or more increases rapidly, and the difference in thermal expansion with a lead frame made of metal increases, so when returning to room temperature, warpage may occur between the heat resistant film and the lead frame. And when warping arises in a heat resistant film and a lead frame in this way, in a resin sealing process, a lead frame cannot be attached to the positioning pin of a metal mold | die, and there exists a possibility of causing a position difference defect.

Therefore, when using a heat resistant film as a base material, it is preferable that it is a heat resistant film whose glass transition temperature is 150 degreeC or more, and it is more preferable that it is 180 degreeC or more from this.

Moreover, it is preferable that the thermal expansion coefficients in 150-250 degreeC of a heat resistant film are 5-50 ppm / degrees C, and it is more preferable that it is 10-30 ppm / degrees C from this. As a heat resistant film which has such a characteristic, the film formed from polyimide, polyamide, polyether sulfone, polyphenylene sulfide, polyether ketone, polyether ether ketone, triacetyl cellulose, polyether imide, etc. can be illustrated. .

Moreover, also when using metal foil as a base material, it is preferable that the thermal expansion coefficient in 150-250 degreeC of metal foil is 5-50 ppm / degreeC, for the same reason as the said heat resistant film, and it is 10-30 ppm / degree C than this. More preferred. Examples of the metal include foils made of gold, silver, copper, platinum, aluminum, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, paradium, cadmium, indium, tin, and lead. Alloy foil which has a main component, or such plating foil can be illustrated.

Moreover, when manufacturing a semiconductor device using the adhesive sheet of this invention, in order to prevent the adhesion trace in an adhesive sheet peeling process, the adhesive strength Sa, sealing resin of a base material and an adhesive layer, a lead frame, and an adhesive layer It is preferable that ratio (adhesive strength ratio) Sa / Sb with adhesive strength Sb to is 1.5 or more. If Sa / Sb is less than 1.5, it is not preferable because adhesion traces are likely to occur in the adhesive sheet peeling step. In addition, in order to make adhesive strength ratio Sa / Sb 1.5 or more, in the case of a heat resistant film, before forming an adhesive bond layer, the surface of the side which forms the adhesive bond layer of a heat resistant film is corona treatment, a plasma treatment, and a primer treatment. It is very preferable to carry out the treatment which raises the adhesive strength Sa between a heat resistant film and an adhesive bond layer, such as a sandblast, beforehand. In the case of the metal foil, the metal foil is classified into a rolled metal foil and an electrolytic metal foil by the manufacturing method. However, in order to make the adhesive strength ratio Sa / Sb 1.5 or more, the side of the surface roughened simultaneously with the use of the electrolytic metal foil is used. It is preferable to provide and adjust an adhesive bond layer on the surface. Moreover, it is preferable to use an electrolytic copper foil especially among electrolytic metal foil.

Moreover, since the adhesive strength at 150-200 degreeC after hardening of the adhesive bond layer with respect to a lead frame is 0.03-5 N / cm can prevent a mold flash, it is preferable. If it is 0.03 N / cm or more, mold flash hardly occurs, and if it is 5 N / cm or less, adhesion traces hardly occur. Moreover, it is preferable in the manufacturing process that the adhesive strength of normal temperature in the unhardening of the adhesive bond layer with respect to a lead frame is 0.98 N / cm or more. It is because it is hard to peel an adhesive bond layer from a lead frame at the time of conveyance in a manufacturing process at 0.98 N / cm or more. In addition, the detail of a measuring method is demonstrated in the Example mentioned later.

EMBODIMENT OF THE INVENTION Hereinafter, the adhesive bond layer with which the adhesive sheet for manufacture of the 1st semiconductor device of this invention is demonstrated.

The adhesive layer with which the adhesive sheet for semiconductor device manufacture of this invention is equipped contains the thermosetting resin component (a) and the thermoplastic resin component (b) which comprise the base [main component (matrix)] of an adhesive, Furthermore, a fluorine additive (c). That is, the adhesive layer always contains a fluorine-based additive (c), and further includes a thermosetting resin component (a) and a thermoplastic resin component (b) different in kind (chemical structure or molecular weight) from the fluorine-based additive (c). It shows what is necessarily comprised by three or more components as a thing.

The total amount of the thermosetting resin component (a) and the thermoplastic resin component (b) is 95 parts by mass or more, preferably 97 to 99.9 parts by mass in 100 parts by mass of the adhesive layer. Above the lower limit, the function as an adhesive layer can be sufficiently obtained.

0.05-2 are preferable and, as for mass ratio (a) / (b) of a thermosetting resin component (a) and a thermoplastic resin component (b), 0.3-1.6 are more preferable. (a) / (b) is the said range, and the balance of both is favorable and the effect which improves the separation and cohesion force of components can be acquired.

In addition, the thermosetting resin component (a) and / or the thermoplastic resin component (b) may contain a fluororesin. At this time, when (a) / (b) is 2 or less, the resin component containing fluorine and the resin component containing no fluorine are not separated at the time of paint preparation, and an adhesive bond layer is easily formed. When (a) / (b) is 0.05 or more, the cohesion force of an adhesive bond layer does not fall and it is difficult to generate | occur | produce a mold flash in a resin sealing process.

Thermosetting Resin Component (a)

Examples of the thermosetting resin component (a) include urea resin, melamine resin, benzoguanamine resin, acetoguanamine resin, phenol resin, resorcinol resin, xylene resin, furan resin, unsaturated polyester resin, diallyl phthalate resin and isocyanate. Nat resin, epoxy resin, maleimide resin, nadiimide resin, etc. can be illustrated. Such resins may be used alone or in combination of two or more thereof.

Among such thermosetting resins, in order to obtain a high elastic modulus at the treatment temperature in the wire bonding step and to obtain an adhesive layer having a high adhesive strength with the lead frame at the treatment temperature in the resin encapsulation step, epoxy resin and It is preferable to contain at least 1 sort (s) of a phenol resin.

Fluorine resin can also be used as a thermosetting resin component (a). The fluorine resin as the thermosetting resin component (a) has a different chemical structure from the fluorine-based additive (c) which is an essential component, and the amount of addition thereof is also different.

Examples of the fluororesin which is a thermosetting resin component (a) include urea resin, melamine resin, benzoguanamine resin, acetoguanamine resin, phenol resin, resorcinol resin, xylene resin, furan resin, unsaturated polyester resin and diallyl phthalate resin. Fluorine is introduced into thermosetting resin components such as isocyanate resins, epoxy resins, maleimide resins, nadiimide resins, or vinylidene difluoride, hexafluoropropylene, tetrafluoroethylene, perfluoromethyl vinyl ether, and the like. The copolymer which superposed | polymerized the monomer which has a functional group (reactive group), and the copolymer which combined such 2 or more types can be illustrated. Moreover, the copolymer formed by adding and polymerizing ethylene, propylene, alkyl vinyl ether, etc. may be sufficient. Among these, the amount of fluorine contained in the fluorine-containing olefin resin having a functional group is particularly preferable, since the resistance to plasma cleaning before wire bonding is high.

More specifically, it is a copolymer formed by superposing | polymerizing the monomer raw material containing hydrocarbon type monomers, such as a fluoroolefin, vinyl ether, and a vinyl ester, and the fluorine resin which has functional groups, such as a hydroxyl group, a carboxy group, and an epoxy group, is mentioned.

The fluorine resin which has the said functional group can be obtained by mix | blending and copolymerizing the monomer which has a functional group with the said raw material monomer, for example. Moreover, after manufacturing fluororesin which has unsaturated bonds, such as a vinyl group, it can also be obtained by introducing functional groups, such as an epoxy group, into this unsaturated bond.

As a monomer which has a functional group, the monomer which has a vinyl bond and functional groups, such as acrylic acid and methacrylic acid, is mentioned, for example.

Various products are sold for such fluorine resins.

Among them, in particular, copolymers obtained by polymerizing monomer raw materials including fluoroolefins and vinyl ethers and / or polymerizing monomer raw materials including fluoroolefins and vinyl esters in order to prevent mold resin leakage and to be peelable without adhesion traces. On the other hand, the fluorine resin which has functional groups, such as a hydroxyl group, a carboxy group, and an epoxy group, is preferable.

As a much more desirable thing, specifically

A copolymer formed by copolymerizing trifluoroethylene with at least one monomer selected from cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether, and having a functional group;

A copolymer formed by copolymerizing trifluoroethylene, at least one monomer selected from alkyl vinyl ether and aryl alcohol, and having a functional group;

It is a copolymer formed by copolymerizing trifluoroethylene, an aliphatic carboxylic acid vinyl ester, and 1 or more types of monomers chosen from hydroxyalkyl vinyl ester, and resin which has a functional group, etc. are mentioned.

As what is marketed among these, the fluoro ethylene vinyl ether copolymer (Asahi Glass Co., Ltd. brand name: luminopron; functional group is a hydroxyl group, a carboxyl group) etc. which have a functional group are mentioned, for example.

When it contains the fluorine resin illustrated above, the content is 5-40 mass parts with respect to 100 mass parts of adhesive bond layers, It is preferable that it is 20-30 mass parts preferably. By setting it as 5 mass parts or more, peelability becomes more favorable and it can prevent that a sticking trace is produced. On the other hand, by setting it as 40 mass parts or less, compatibility with other resin components improves and it is advantageous on manufacture.

Thermoplastic resin component (b)

As the thermoplastic resin component (b), an acrylonitrile-butadiene copolymer (NBR), an acrylonitrile-butadiene-styrene resin (ABS), a styrene-butadiene-ethylene resin (SEBS), a styrene-butadiene-styrene resin (SBS ), Polybutadiene, polyacrylonitrile, polyvinyl butyral, polyamide, polyamideimide, polyimide, polyester, polyurethane, acryl rubber and the like. These thermoplastic resins may be used either alone or in combination.

Fluorine resin can also be mix | blended with a thermoplastic resin component (b). As a fluororesin mix | blended with a thermoplastic resin component (b), an acrylonitrile- butadiene copolymer (NBR), an acrylonitrile- butadiene- styrene resin (ABS), a styrene-butadiene- ethylene resin (SEBS), a styrene-butadiene -Thermoplastic resins such as styrene resin (SBS), styrene-ethylene-butylene resin, polybutadiene, polyacrylonitrile, polyvinyl butyral, polyamide, polyamideimide, polyimide, polyester, polyurethane, acrylic rubber, etc. Examples thereof include fluorine-introduced components, polymers of olefin resins such as vinylidene difluoride, hexafluoropropylene, tetrafluoroethylene, and perfluoromethyl vinyl ether, or a combination of two or more thereof. . Moreover, the copolymer which added ethylene, propylene, alkyl vinyl ether, etc. may be sufficient. In particular, an olefin resin is more preferable in that the amount of fluorine can be increased and the durability against plasma cleaning before wire bonding is high.

More specifically, the copolymer formed by superposing | polymerizing the monomer raw material containing hydrocarbon type monomers, such as a fluoroolefin, vinyl ether, and a vinyl ester, is mentioned.

Especially, since it can be made to prevent mold resin leakage prevention and adhesion traces, it is a polymer made by superposing | polymerizing the monomer raw material containing a fluoroolefin and vinyl ether, and / or polymerizing the monomer raw material containing a fluoroolefin and vinyl ester. Copolymers are preferred.

Particularly very preferred, specifically

Copolymers formed by copolymerizing trifluoroethylene with at least one monomer selected from cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether;

Copolymers obtained by copolymerizing trifluoroethylene with at least one monomer selected from alkyl vinyl ether and aryl alcohol;

And copolymers obtained by copolymerizing one or more monomers selected from trifluoroethylene, aliphatic carboxylic acid vinyl esters, and hydroxyalkyl vinyl esters.

When containing a fluororesin in a thermoplastic resin component (b), the content is 5-40 mass parts with respect to 100 mass parts of adhesive bonds, It is preferable that it is 20-30 mass parts preferably. Since it is 5 mass parts or more, peelability becomes more favorable and adhesion traces are less likely to arise. On the other hand, by setting it as 40 mass parts or less, compatibility with other resin components becomes more favorable and it is advantageous in manufacture.

Moreover, when a reactive elastomer is mix | blended with a thermoplastic resin component (b), since the effect of this invention improves, it is preferable.

As reactive elastomer, it is an elastic resin which has reactivity which has structural units derived from functional groups, such as a carboxy group, an amino group, a vinyl group, and an epoxy group, and acid anhydride monomers, such as maleic anhydride.

The reactive elastomer can be produced by copolymerizing a monomer having a functional group or an acid anhydride monomer when producing an elastic resin. Moreover, after manufacturing elastic resin which has unsaturated bonds, such as a vinyl bond, it can manufacture by introducing functional groups, such as an epoxy group, into this unsaturated bond. Moreover, as a monomer which has a functional group, the monomer which has a vinyl bond and functional groups, such as acrylic acid and methacrylic acid, is mentioned, for example.

Specifically, carboxyl group-containing styrene-butadiene copolymer, carboxyl group-containing styrene-isoprene copolymer, carboxyl group-containing styrene-butadiene saturated copolymer, carboxyl group-containing styrene-isoprene saturated copolymer, carboxyl group-containing styrene-ethylene-butene-styrene copolymer, Carboxyl group-containing styrene-ethylene-butene-styrene saturated copolymer, carboxyl group-containing acrylonitrile-butadiene copolymer, amino-modified polyol resin, amino-modified phenoxy resin, amino-modified acrylonitrile-butadiene copolymer, polyvinyl butyral resin, Polyvinyl acetal resin, carboxyl group-containing acrylonitrile-butadiene copolymer, hydrogenated carboxyl group-containing acrylonitrile-butadiene copolymer, carboxyl group-containing acrylic rubber, maleic anhydride-containing styrene-butadiene copolymer, maleic anhydride-containing styrene-ethylene-butene -Styrene aerial A copolymer, a hydroxy terminal terminal saturated copolymer polyester resin, a carboxy group terminal saturated copolymer polyester resin, an epoxy group containing styrene block copolymer, maleic anhydride containing styrene- ethylene- butylene copolymer, etc. are mentioned. These reactive elastomers can be used 1 type or in mixture of 2 or more types. In addition, "maleic anhydride containing" shows what copolymerized maleic anhydride.

The following are mentioned as what is marketed among these.

Examples of the carboxyl group-containing acrylonitrile-butadiene copolymer include Nippon Zeon, trade name: Nipol'1072J, the company's trade name: Nipol 'DN631, Ube Kosan's trade name: Hycar® CTBN, JSR's trade name: PNR-1H, and the like.

Examples of the amino group-containing acrylonitrile-butadiene copolymer include Ubekosan Co., Ltd. brand name: Hycar ATBN.

As a maleic anhydride containing styrene- ethylene- butylene copolymer, Asahi Kasei Co., Ltd. brand name: Toughtec M series etc. are mentioned.

As an epoxy-group-containing styrene-type block copolymer, the brand name: Epofren made by Daicel Chemical Industries, Ltd. is mentioned.

In particular, maleic anhydride-containing styrene-ethylene-butylene copolymers are preferable in order to prevent mold resin leakage and to be peelable without adhesion traces. In the copolymer, the mass ratio of maleic anhydride: styrene: ethylene-butylene (total of ethylene-butylene) is preferably 0.3 to 3:10 to 40:60 to 90, particularly 0.5 to 1:20. It is preferable that it is -30: 70-80.

It is preferable to use a reactive elastomer in the range of 30-95 mass parts with respect to 100 mass parts of adhesive bond layers, Especially preferably, it is 40-90 mass parts. At 30 mass parts or more, it can make it hard to produce a mold flash and a sticking trace. By setting it as 95 mass parts or less, peelability can improve more and it can prevent that adhesion traces arise more.

When the mass average molecular weight of the thermoplastic resin component (b) is 2,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 10,000 to 500,000, the cohesive force of the adhesive layer can be increased, and the adhesion traces in the adhesive sheet peeling step It is preferable to be able to prevent more.

Fluorine-based additive (c)

It is preferable that a fluorine additive (c) is resin (it may be oligomer), and a fluorine-containing graft polymer, a fluorine-containing block copolymer, a fluorine-containing aliphatic polymer ester, etc. are mentioned. The fluorine additive (c) may be used alone or in combination of two or more thereof. It is preferable that these are thermoplastic resins.

As a fluorine-containing graft polymer, the brand name of the chemical product made by Soken Chemical Co., Ltd. which is a fluorine-acryl-type graft polymer: Chemitri 'LF-700 etc. are mentioned. The fluorine-containing acrylic graft polymer is composed of a hepatic polymer and a plurality of terpolymers grown from the hepatic polymer, the hepatic polymer is an acrylic polymer, and the terpolymer is a polymer containing fluorine. will be.

As a fluorine-containing block copolymer, the block copolymer which consists of an alkyl fluoride-containing polymer segment and an acryl-type polymer segment is a brand name of a Nippon Oil Holding Co., Ltd. brand name: Modifa F series, for example, Modifa F200, Modifa F220, Modifa F2020, It is marketed as Modpa F3035 and Modpa F600.

Moreover, as a fluorine-containing aliphatic type-polymer ester, what has a characteristic as a nonionic surfactant is preferable, The brand name made by 3M Corporation: Novekk FC-4430, etc. are mentioned.

Among them, a fluorine-containing graft polymer or a fluorine-containing block copolymer is particularly preferable because it can be prevented from leaking and preventing mold resin leakage.

The compounding quantity of a fluorine-type additive (c) becomes like this. Preferably it is 0.1-5 mass parts, More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of adhesive bond layers. By making it more than a lower limit, the effect of this invention improves. It is preferable to make it below an upper limit from a balance with the material which comprises the base of an adhesive bond layer, saturation of an effect, and an economical viewpoint.

Moreover, in order to adjust the thermal expansion coefficient, thermal conductivity, surface tuck, adhesiveness, etc. of an adhesive bond layer, it is preferable to add an inorganic or organic filler to an adhesive bond layer. As the inorganic filler, pulverized silica, dissolved silica, alumina, titanium oxide, beryllium oxide, magnesium oxide, calcium carbonate, titanium nitride, silicon nitride, boron nitride, titanium boride, tungsten boride, silicon carbide, titanium carbide, carbide Examples thereof include fillers made of zirconium, molybdenum carbide, mica, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide, or the like having trimethylsiloxane group introduced on the surface thereof. Moreover, as an organic filler, the filler which consists of polyimide, polyamideimide, polyether ether ketone, a polyether imide, a polyester imide, nylon, a silicone resin, etc. can be illustrated.

Next, the adhesive layer with which the adhesive sheet for manufacturing a second semiconductor device is described will be described.

The adhesive bond layer of this invention contains a fluororesin. Here, the fluororesin refers to a resin containing a fluorine element as a constituent component in a broad sense as described above.

It is preferable that an adhesive bond layer contains a thermosetting resin component (a1) and a thermoplastic resin component (b1), and contains either a thermosetting resin component (a1) or a thermoplastic resin component (b1). In this case, the mass ratio (a1) / (b1) of the thermosetting resin component (a1) and the thermoplastic resin component (b1) is preferably 0.05 to 0.43, more preferably 0.11 to 0.25.

When (a1) / (b1) is 0.43 or less, the resin component containing fluorine and the resin component containing no fluorine are hard to be separated when producing a paint, and an adhesive bond layer is easy to form. When (a1) / (b1) is 0.05 or more, the cohesion force of an adhesive bond layer hardly falls, and therefore, mold flash hardly arises in a resin sealing process.

Thermosetting resin component (a1)

As the thermosetting resin component (a1), urea resin, melamine resin, benzoguanamine resin, acetoguanamine resin, phenol resin, resorcinol resin, xylene resin, furan resin, unsaturated polyester resin, diallyl phthalate resin, isocyanate Nat resin, epoxy resin, maleimide resin, nadiimide resin, etc. can be illustrated. In addition, these resin may be used independently and may use 2 or more types together. In particular, by containing at least one of an epoxy resin and a phenol resin, it has a high elastic modulus at the treatment temperature in the wire bonding process and has a high adhesive strength with the lead frame at the treatment temperature in the resin encapsulation process. It is preferable because an adhesive bond layer can be obtained.

Moreover, the thermosetting resin component containing fluorine can also be used as said thermosetting resin component (a1). As a thermosetting resin component containing fluorine, fluorine is introduced into the thermosetting resin component or an olefin resin such as vinylidene difluoride, hexafluoropropylene, tetrafluoroethylene or perfluoromethyl vinyl ether has a reactive functional group. The polymer containing a monomer or the copolymer which combined these 2 or more types can be illustrated. Moreover, the copolymer which added ethylene, propylene, alkyl vinyl ether, etc. may be sufficient. Among these, especially a fluorine-containing olefin resin is more preferable at the point that the amount of fluorine contained is high and resistance to plasma cleaning before wire bonding is high.

Thermoplastic resin component (b1)

As the thermoplastic resin component (b1), an acrylonitrile-butadiene copolymer (NBR), an acrylonitrile-butadiene-styrene resin (ABS), a styrene-butadiene-ethylene resin (SEBS), a styrene-butadiene-styrene resin (SBS ), Polybutadiene, polyacrylonitrile, polyvinyl butyral, polyamide, polyamideimide, polyimide, polyester, polyurethane, acrylic rubber and the like. In addition, these resin may be used independently and may use 2 or more types together.

Moreover, the thermoplastic resin containing fluorine can also be used as said thermoplastic resin component (b1). Examples of the thermoplastic resin component containing fluorine include fluorine introduced into the thermoplastic resin component, polymers such as vinylidene difluoride, hexafluoropropylene, tetrafluoroethylene, and perfluoromethyl vinyl ether, or two kinds, as olefin resins. The copolymer which combined the above can be illustrated. Moreover, the copolymer which added ethylene, propylene, alkyl vinyl ether, etc. may be sufficient. In particular, an olefin resin is more preferable because it can increase the amount of fluorine and thus has high durability against plasma cleaning before wire bonding.

In addition, when the mass average molecular weight of the thermoplastic resin component (b1) is 2,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 10,000 to 500,000, the cohesive force of the adhesive layer can be increased and the adhesive sheet peeling process It is preferable because the adhesion trace can be further prevented.

Also in the adhesive layer included in the second adhesive sheet, in order to adjust the coefficient of thermal expansion, thermal conductivity, surface wrinkles, adhesiveness, and the like, similarly to the adhesive layer included in the first adhesive sheet, an inorganic or organic filler is used in the adhesive layer. Preference is given to adding.

Next, the adhesive layer with which the adhesive sheet for 3rd semiconductor device manufacture is provided is demonstrated.

The adhesive layer of the adhesive sheet for semiconductor device manufacture of the present invention contains a fluororesin and a reactive elastomer. Here, as described above, the fluorine resin refers to a resin containing a fluorine element as a constituent component in a broad sense.

Fluorine Resin

As said fluororesin, the polymer which contained (copolymerized) the monomer which has a functional group (reactive group) in olefin resin, such as vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, perfluoromethyl vinyl ether, or these two types The copolymer etc. which combined the above can be illustrated. Moreover, the copolymer formed by adding and polymerizing ethylene, propylene, alkyl vinyl ether, etc. may be sufficient. Among these, especially the fluorine-containing olefin resin which has a functional group is more preferable at the point that the amount of fluorine to contain and high resistance to the plasma cleaning before wire bonding are high.

More specifically, it is a copolymer formed by superposing | polymerizing the monomer raw material containing hydrocarbon type monomers, such as a fluoroolefin, vinyl ether, and a vinyl ester, and the fluorine resin which has functional groups, such as a hydroxyl group, a carboxy group, and an epoxy group, is mentioned.

The fluorine resin which has the said functional group can be obtained by mix | blending and copolymerizing the monomer which has a functional group in addition to the said monomer, for example in a raw material monomer. Moreover, after manufacturing fluorine resin which has unsaturated bonds, such as a vinyl group, it can obtain by introducing functional groups, such as an epoxy group, into unsaturated bonds, such as this vinyl group.

As a monomer which has a functional group, the monomer which has a vinyl bond and functional groups, such as acrylic acid and methacrylic acid, is mentioned, for example.

As such a fluororesin, various products are sold.

Among them, in particular, copolymers obtained by polymerizing monomer raw materials containing fluoroolefins and vinyl ethers and / or polymerizing monomer raw materials including fluoroolefins and vinyl esters for preventing mold resin leakage and peeling without adhesion traces. On the other hand, the fluorine resin which has functional groups, such as a hydroxyl group, a carboxy group, and an epoxy group, is preferable.

Particularly preferred, specifically

A copolymer formed by copolymerizing trifluoroethylene with at least one monomer selected from cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether, and having a functional group;

A copolymer formed by copolymerizing trifluoroethylene, at least one monomer selected from alkyl vinyl ether and aryl alcohol, and having a functional group;

A copolymer formed by copolymerizing trifluoroethylene, an aliphatic carboxylic acid vinyl ester, and at least one monomer selected from hydroxyalkyl vinyl esters, and resins having a functional group.

As what is marketed among these, the fluoroethylene vinyl ether copolymer which has a functional group (trade name: Lumifuron by Asahi Glass, Inc .; a functional group is a hydroxyl group, a carboxyl group), etc. are mentioned, for example.

The compounding quantity of the fluororesin mentioned above becomes like this. Preferably it is 5-40 mass parts, More preferably, it is 20-30 mass parts with respect to 100 mass parts of adhesive bond layers. By setting it as 5 mass parts or more, peelability improves more and adhesion traces can be prevented. On the other hand, in 40 mass parts or less, compatibility with other resin components improves and it is advantageous also on manufacture.

(Reactive elastomer)

As a reactive elastomer, it is an elastic resin which has reactivity which has structural units derived from functional groups, such as a carboxy group, an amino group, a vinyl group, an epoxy group, and acid anhydride monomers, such as maleic anhydride.

The reactive elastomer can be produced by copolymerizing a monomer having a functional group or an acid anhydride monomer when producing an elastic resin. Moreover, after manufacturing elastic resin which has unsaturated bonds, such as a vinyl bond, it can manufacture by introducing functional groups, such as an epoxy group, into unsaturated bonds, such as this vinyl group. Moreover, as a monomer which has a functional group, the monomer which has a vinyl bond and functional groups, such as acrylic acid and methacrylic acid, is mentioned, for example.

Specifically, carboxyl group-containing styrene-butadiene copolymer, carboxyl group-containing styrene-isoprene copolymer, carboxyl group-containing styrene-butadiene saturated copolymer, carboxyl group-containing styrene-isoprene saturated copolymer, carboxyl group-containing styrene-ethylene-butene-styrene copolymer, Carboxyl group-containing styrene-ethylene-butene-styrene saturated copolymer, carboxyl group-containing acrylonitrile-butadiene copolymer, amino-modified polyol resin, amino-modified phenoxy resin, amino-modified acrylonitrile-butadiene copolymer, polyvinyl butyral resin, Polyvinyl acetal resin, carboxyl group-containing acrylonitrile-butadiene copolymer, hydrogenated carboxyl group-containing acrylonitrile-butadiene copolymer, carboxyl group-containing acrylic rubber, maleic anhydride-containing styrene-butadiene copolymer, maleic anhydride-containing styrene-ethylene-butene -Styrene Polymer, hydroxy-terminal saturated copolymer polyester resin, carboxy-terminal saturated copolymer polyester resin, epoxy group-containing styrene block copolymer, maleic anhydride-containing styrene-ethylene-butylene copolymer, and the like. Containing "means copolymerizing maleic anhydride.

The following are mentioned as what is marketed among them.

Examples of the carboxyl group-containing acrylonitrile-butadiene copolymer include Nippon Zeon, trade name: Nipol'1072 J, the company's trade name: Nipol 'DN631, Ube Kosan's trade name: Hycar' CTBN, JSR's trade name: PNR-1H, and the like.

Examples of the amino group-containing acrylonitrile-butadiene copolymer include Ubekosan Co., Ltd. brand name: Hycar ATBN.

As a maleic anhydride containing styrene- ethylene- butadiene copolymer, Asahi Kasei Co., Ltd. brand name: Tough Tech M series etc. are mentioned.

As an epoxy-group-containing styrene-type block copolymer, the brand name: Epofuren etc. made from Daicel Chemical Industries, Ltd. are mentioned.

Among them, maleic anhydride-containing styrene-ethylene-butylene copolymers are preferable because they can be peeled off particularly without preventing mold resin leakage and adhesion traces. In the copolymer, the mass ratio of maleic anhydride: styrene: ethylene-butylene (total of ethylene-butylene) is preferably 0.3 to 3:10 to 40:60 to 90, and more preferably 0.5 to 1 It is preferable that it is 20: 30: 70-80.

The reactive elastomer is preferably 30 to 95 parts by mass, more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the adhesive layer. By setting it as 30 mass parts or more, mold flash and adhesion traces can be prevented. On the other hand, by using 95 mass parts or less, peelability improves more and it is possible to prevent adhesion traces from occurring.

The peeling force of an adhesive sheet can be improved further by including a fluorine-type additive in an adhesive bond layer. As the fluorine additive, the same fluorine additive as the fluorine additive (c) contained in the first adhesive layer can be used.

In addition, the adhesive layer may contain a curing accelerator such as a thermosetting resin, a thermoplastic resin, a fluororesin, a curing agent crosslinking with a reactive elastomer, a dehydration catalyst, or the like.

The thermosetting resin component and the thermoplastic resin may be a thermosetting resin and a thermoplastic resin contained in the adhesive layer included in the first adhesive tape.

Moreover, also in the adhesive bond layer with which a 3rd adhesive sheet is equipped, in order to adjust thermal expansion coefficient, thermal conductivity, surface wrinkles, adhesiveness, etc. similarly to the adhesive layer with a 1st adhesive sheet, an inorganic or organic filler is carried out to an adhesive bond layer. Preference is given to adding.

Next, the method of forming the said 1st thru | or 3rd adhesive bond layer in one side of a base material is demonstrated. The casting method which coats an adhesive agent directly on a base material, and drys, the lamination method which apply | coats an adhesive agent on a release film once, and after drying, transfers to a base material is very preferable.

Moreover, it is preferable that a thermosetting resin component and a thermoplastic resin component are used with an organic solvent. For example, aromatics such as toluene, xylene, chlorbenzene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, non-flotone polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone And organic solvents such as tetrahydrofuran. These organic solvents can be used individually or in mixture of 2 or more types. When using an organic solvent, it is preferable to melt | dissolve 1 mass% or more, preferably 5 mass% or more of a thermosetting resin and a thermoplastic resin component, and use it as an adhesive coating liquid.

In particular, when the adhesive layer contains a thermosetting resin component, it is preferable to mix | blend hardening agents, such as 2-ethyl- 4-methylimidazole, in an adhesive agent coating liquid, and to mix | blend a hardening accelerator further as needed.

It is good also as a structure which sticks a peelable protective film on the adhesive bond layer of the adhesive sheet of this invention, and peels a protective film immediately before manufacture of a semiconductor device. In this case, the adhesive layer can be prevented from being damaged until after the adhesive sheet is manufactured and used. As the protective film, any film may be used as long as it has releasability. For example, a film such as polyester, polyethylene, polypropylene, polyethylene terephthalate, or a film obtained by releasing the surface of these films with a silicone resin or a fluorine compound, etc. Can be illustrated.

Moreover, the storage modulus after hardening of the said adhesive bond layer in the whole temperature range of 150 degreeC-250 degreeC is 0.1 Mpa or more, Preferably it is 1 Mpa or more, It is preferable that it is 5 Mpa or more further. In addition, after hardening here means the adhesive bond layer of the state heat-processed in the die attach process. In the wire bonding process for manufacturing a semiconductor device, in order to connect a semiconductor device and a lead frame using a bonding wire, both ends of the bonding wire are heated at 150 to 250 ° C. and fused with ultrasonic waves of 60 to 120 kHz. , The adhesive layer of the adhesive sheet located directly below the lead frame is exposed to high temperature by the heating, it becomes low elasticity and easily absorbs the ultrasonic waves, and as a result, the lead frame vibrates, so that wire bonding defects tend to occur. In the case of the adhesive sheet having the adhesive layer having the storage modulus, such a problem hardly occurs.

(Method of manufacturing semiconductor device)

With reference to FIG. 1 and FIG. 2, an example of the method of manufacturing a semiconductor device using the adhesive sheet of this invention is demonstrated. Hereinafter, the case where QFN is manufactured as a semiconductor device is demonstrated as an example.

1 is a schematic plan view of a lead frame as viewed from the side on which the semiconductor element is mounted, and FIGS. 2A to 2F are process drawings showing a method of manufacturing a QFN from the lead frame shown in FIG. The lead frame is an enlarged schematic sectional view of the AA 'line of FIG.

First, the lead frame 20 of the schematic structure shown in FIG. 1 is prepared. The lead frame 20 includes a plurality of island-shaped semiconductor element mounting portions 21 (die pad portions) for mounting semiconductor elements such as IC chips, and includes a plurality of leads according to the outer circumference of each semiconductor element mounting portion 21. 22) is excreted. Next, as shown in Fig. 2 (a), in the adhesive sheet bonding step, the adhesive layer (not shown) side of the adhesive sheet 10 of the present invention on one side (lower surface) of the lead frame 20 It sticks so that it may become the lead frame 20 side. Moreover, as a method of sticking the adhesive sheet 10 to the lead frame 20, the lamination method etc. are very preferable. Next, as shown in FIG. 2 (b), in the die attach step, the semiconductor such as an IC chip is formed from the side where the adhesive sheet 10 is not stuck to the semiconductor element mounting portion 21 of the lead frame 20. The element 30 is mounted using a die attach agent (not shown).

Next, with the heat history acting right before the wire bonding, the outgas component generated by the adhesive sheet, the die attach agent, or the like is attached to the lead frame, and the wire bonding step is performed in order to prevent a decrease in yield due to poor bonding of the wire. Beforehand, the lead frame on which the adhesive sheet, the die attach agent, and the IC chip are mounted may be plasma cleaned.

Next, as shown in FIG. 2 (c), in the wire bonding step, the semiconductor element 30 and the leads 22 of the lead frame 20 are electrically connected to each other through a bonding wire 31 such as a gold wire. Connect. Next, as shown in Fig. 2 (d), in the resin encapsulation step, the semiconductor device in the middle of manufacturing is placed in a mold as shown in Fig. 2 (c), and the encapsulating resin (molding material) is used. By transfer mold (molding), the semiconductor element 30 is sealed by the sealing resin 40.

Next, as shown in FIG. 2E, in the adhesive sheet peeling process, the plurality of QFNs 50 are arranged by peeling the adhesive sheet 10 from the sealing resin 40 and the lead frame 20. The QFN unit 60 can be formed. Finally, as shown in FIG. 2 (f), in the dicing step, the QFN units 60 can be diced along the outer periphery of each QFN 50 to produce a plurality of QFNs 50.

EXAMPLE

Although an Example demonstrates this invention further in detail below, this invention is not limited to these Examples.

First, the evaluation method of the obtained adhesive bond layer or an adhesive sheet is demonstrated. Evaluation was performed as follows.

<Measurement of Storage Modulus>

After applying the adhesive solution obtained in each Example and the comparative example on a release film, it dried under the same drying conditions as when manufacturing an adhesive sheet, and heat-processed by the die-attach process heat treatment conditions (2 hours at 175 degreeC). Was performed and the adhesive bond layer release film was produced.

Moreover, the adhesive agent was applied and dried so that the thickness after drying might be 0.1 mm. The obtained sample was cut into 5 mm x 30 mm, and the frequency 11 was used using the elasticity modulus measuring device (Leo Vibron DDV-II by Orient Tech). The measurement was carried out at Hz, a heating rate of 3 ° C./min, and a measurement temperature range of 150 ° C. to 250 ° C., and the results are shown in the following table. In addition, the numerical value in the following table | surface shows the minimum value of the storage elastic modulus in the measurement temperature range 150 degreeC-250 degreeC.

<Evaluation of the adhesive sheet>

1. Bad wire bonding

The adhesive sheets obtained in the examples and the comparative examples were subjected to QFN lead frames (Au-Pd-Ni-plated Cu lead frames, 4 × 16 matrix arrays and packages in total) of external dimensions of 200 mm × 60 mm. 10 mm x 10 mm, 84 pins) by the lamination method. Next, a dummy chip (6 mm x 6 mm, thickness 0.4 mm) on which aluminum was deposited using an epoxy die attach agent was mounted on the semiconductor element mounting portion of the lead frame.

Thereafter, without performing plasma cleaning, using a wire bonder (manufactured by Shinkawa Co., Ltd., UTC-470 BI), the heating temperature was 210 ° C, the US POWER was 30, the load was 0.59 N, and the treatment time was 10 msec / pin. The dummy chip and the lead were electrically connected by gold wires. The obtained 64 semiconductor devices were inspected, and the number of semiconductor devices in which lead side connection defects occurred was detected as the number of occurrences of wire bonding defects.

In addition, in some examples and comparative examples, plasma cleaning was performed after mounting on the semiconductor element mounting portion of the lead frame. Plasma cleaning conditions are using gas: Ar, gas flow rate: 45 sccm, RF output: 450 W, processing time: 5 minutes using a plasma etching apparatus (trade name: V1000 manufactured by Yamatogagaku Co., Ltd.).

2.molded flash

The mold flash was evaluated using the lead frame after evaluating the wire bonding defect. The dummy chip was encapsulated by a transfer mold (molding) using an epoxy-based mold agent (biphenyl epoxy clock, filler amount of 85% by mass) at a heating temperature of 180 ° C, a pressure of 10 MPa, and a processing time of 3 minutes. Sealed by. 64 semiconductor devices after resin sealing were inspected, and the number of semiconductor devices in which the sealing resin was attached to the external connection portion of the lid (the surface of the adhesive sheet side of the lead) was detected as the number of mold flashes generated.

3. Adaptation

The adhesion trace evaluation was performed using the lead frame after evaluating a mold flash. First, the adhesive sheet was peeled from the lead frame under conditions of a peel rate of 500 mm / min. After peeling the adhesive sheet, 64 semiconductor devices were inspected, and the number of semiconductor traces in which the adhesive was adhered to the adhesive sheet peeling surface including the external connection portion of the lid and the wetted surface was defined as the number of adhered traces.

4. Adhesive strength

The adhesive sheet obtained in each Example and the comparative example was cut | disconnected by 1 cm width, and it rolls to the copper plate (trade name: MF-202 by Mitsubishi Metex company make: Mitsubishi Metex company make: brand name: MF-202) of 50 mm x 100 mm x 0.25 mm, and the plate which plated gold plated. Compressed by lamination. Then, after heat history equivalent to a die attach cure (175 ° C. × 1 hour) and a bite resin cure (180 ° C. × 4 hour), the temperature was returned to room temperature. These plates were heated to 150 ° C, and the peel strength when the adhesive layer of the obtained laminate was pulled off in the 90 ° C direction with respect to the plate was measured. Similarly, this peeling strength was measured by raising the heating temperature of the plate every 5 ° C from 150 ° C to 200 ° C. And the minimum value in the peeling strength in each measurement temperature of 150-200 degreeC was made into the adhesive strength of an adhesive sheet.

5.Measure the outgas amount of the adhesive sheet

The mass reduction rate of the adhesive sheet was measured at a temperature rising rate of 10 ° C./min and a measurement temperature of 30 to 300 ° C. using a thermal mass reduction measuring device (manufactured by Seiko Instruments Co., Ltd., EZSTAR6000 series, TG / DTA6300). The smaller the mass reduction rate, the smaller the outgas amount.

Examples 1-4 and Comparative Examples 1-5

As shown in Table 1 below, an adhesive was prepared to prepare an adhesive sheet, and the obtained adhesive layer and the adhesive sheet were evaluated.

That is, it mixed with toluene by the composition and compounding ratio (mass part) shown in Table 1, and produced the adhesive solution. Next, using a polyimide resin film (trade name: manufactured by Toray DuPont, thickness 25 μm, glass transition temperature 300 ° C. or higher, thermal expansion coefficient 16 ppm / ° C.) as a heat resistant base material thereon, and drying it thereon to have a thickness of 6 μm. After apply | coating the said adhesive solution, it dried at 120 degreeC for 5 minutes, and obtained the adhesive sheet which has an adhesive bond layer.

Then, the above-mentioned wire bonding defects, mold flashes, adhesion traces, adhesive strength, and outgas amount measurements were evaluated for the obtained adhesive sheets, respectively. The evaluation results are shown in Table 2 and Table 3 (outgas amount measurement results).

TABLE 1-1

Example One 2 3 4  Thermosetting Resin Component (a) Epoxy Resin * 1 30 25 25 Phenolic Resin * 2 30 25 25 Fluoroethylene vinyl ether copolymer having a functional group * 9 30  Thermoplastic resin component (b) Non-reactive Elastomer Acrylonitrile Butadiene Copolymer * 3 40 40 Reactive Elastomer Maleic Anhydride-containing Styrene-Ethylene-Butylene Copolymer * 6 50 70 Fluorine-based additive (c) Fluorinated Acrylic Graft Polymer * 4 1.5 0.5 Fluorine-containing block copolymer * 7 0.5 Fluorinated Fatty Acid Polymer Ester * 8 1.5 Hardener 2-ethylene-4-methylimidazole * 5 0.5 0.5 0.5 * 10 One

TABLE 1-2

Comparative example One 2 3 4 5  Thermosetting Resin Component (a) Epoxy Resin * 1 45 35 35 Phenolic Resin * 2 25 35 35 Epoxy Resin * 12 40 Phenolic Resin * 13 20  Thermoplastic resin component (b) Non-reactive Elastomer Acrylonitrile Butadiene Copolymer * 3 40 40 Reactive Elastomer Maleic Anhydride-containing Styrene-Ethylene-Butylene Copolymer * 6 Reactive Elastomer Epoxidized Styrene-Butadiene-Styrene Copolymer * 11 30 30  Etc Silicone Oil * 14 1.5 2 Silicone Rubber * 15 100 Silicone Rubber * 16 0.5 Hardener 2-ethylene-4-methylimidazole * 5 0.5 0.5 0.5 0.5

* 1: Product made in Dainippon Ink, Kogyo Co., Ltd. brand name: HP-7200

* 2: Product made in Nippon Kayakku Co., Ltd. name: TPM

* 3: Product made in Nippon Xeon company: Nippol # 1001

* 4 made in Soken Chemical Co., Ltd. brand name: Chemity 'LF-700 (solid content 7.5 mass%; solvent toluene methyl ethyl ketone)

* 5: Tokyo Kasei Corporation

* 6 made in Asahi Kasei Co., Ltd. Product name: Tough technical center M-1919

* 7: Nippon Oil Co., Ltd. brand name: Modifa F200 (30 mass% of solid content; solvent methyl ethyl ketone methyl isobutyl ketone)

* 8: Product name made in 3M company: Novek FC-4430

* 9 made in Asahi Glass Co., Ltd. Product name: Lumifuron LF916

* 10: Product made in Nippon Polyurethane high school company: Colonate L

* 11 made by Daicel Kagaku Co., Ltd. Product name: EPO FRENCH AT501

* 12: Product made in Japan epoxy resin company: Epicoat 1001

* 13: Product made in Showa Tomb City company name: CKM-2400

* 14: Product made in Shin-Etsu Kagaku Kogyo Co., Ltd. product name: KF-105

* 15: Product made in Torre Dow Corning Corporation: SD4580

* 16: Product made in Torre Dow Corning Corporation: SRX212

TABLE 2

Bad wire bonding () Mold Flash (pcs) Adherence traces occur () Adhesion Strength (N / cm) No gold plating Gold plated   Example One 0 0 0 1.05 0.82 2 0 0 0 0.86 0.74 3 0 0 0 1.30 1.07 4 0 0 0 0.68 0.62   Comparative example One 2 0 63 5.43 4.36 2 One 0 59 6.01 5.71 3 17 0 0 1.26 1.00 4 13 4 0 0.99 0.80 20 32 41 0.64 0.67

TABLE 3

100 ℃ (mass%) 200 ℃ (mass%) 300 ℃ (mass%)  Example One 0.3 0.6 0.8 2 0.2 0.2 0.4 3 0.2 0.2 0.5 4 0.2 0.2 0.3  Comparative example One 0.3 0.7 0.8 2 0.3 0.8 0.9 3 0.7 1.3 1.7 4 0.7 1.3 1.7 5 0.7 1.0 1.4

Examples 5, 6, and 8

The adhesive solution was prepared by mixing toluene with the composition and compounding ratio (mass part) shown in following Table 4. Next, using a polyimide resin film (trade name: manufactured by Toray DuPont, thickness 25 μm, glass transition temperature 300 ° C. or higher, thermal expansion coefficient 16 ppm / ° C.) as a heat resistant base material thereon, and drying it thereon to have a thickness of 6 μm. After apply | coating the said adhesive solution, it dried for 5 minutes at 120 degreeC, and obtained the adhesive sheet of this Example which has an adhesive bond layer.

Examples 7, 10, and 11

The adhesive sheet of this invention was obtained like Example 5 except having changed into the adhesive solution mixed with methyl ethyl ketone by the composition and compounding ratio shown in Table 4 below.

Example 9

An adhesive solution was prepared at the same composition and blending ratio as in Example 5, and then 3/4 ounces of copper foil (trade name: 3EC-VLP manufactured by Mitsui Ginku Kogyo Co., Ltd., thickness: 25 µm, thermal expansion coefficient of 16 ppm / ° C) was used as the heat resistant substrate. It used, the said adhesive solution was apply | coated so that the thickness might be 8 micrometers after drying on the rough surface, and it dried at 120 degreeC for 5 minutes, and obtained the adhesive sheet of this Example which has an adhesive bond layer.

Comparative Examples 6 and 7

A comparative adhesive sheet was obtained in the same manner as in Example 5 except that the adhesive solution mixed with methyl ethyl ketone was changed at the composition and blending ratio shown in Table 4 below.

Subsequently, the adhesive sheets obtained in Examples 5 to 11 and Comparative Examples 6 and 7 were prepared by plasma cleaning or not, and the above-described measurement of storage modulus, poor wire bonding, mold flash, adhesion traces and adhesion were prepared. Intensities were evaluated respectively. Table 5 shows the measurement results.

TABLE 4

Example Comparative example 5 6 7 8 9 10 11 6 7  Thermosetting Resin Component (a) Fluoropolymer * 17 5 20 10 15 5 Epoxy Resin A * 18 10 10 Epoxy Resin B * 19 5 5 Phenolic Resin A * 20 5 5 Phenolic Resin B * 21 5 5  Thermoplastic resin component (b) NBR * 22 95 95 85 Ethylene-methylacrylate-glycidyl methacrylate copolymer resin * 23 80 90 Acrylic acid ester-glycidyl acrylate-acrylonitrile copolymer resin * 24 90 SBR * 25 85 Fluorine rubber * 26 85 90 Curing agent * 27 One One One One One Curing Accelerator * 28 One One One One (a1) / (b1) 0.05 0.25 0.11 0.17 0.05 0.17 0.11 0.17 0.11

* 17: Product made in Asahi Glass Co., Ltd .: Lumifuron LF200F

* 18: Product made in Dainihon Kagaku Kogyo Co., Ltd., brand name: HP-7200

* 19: Product made in Japan epoxy resin company, Brand name: Epicoat 828

* 20: Product made in Showa Tomb City, Brand Name: CKM2400

* 21: Product made in Shin-Nihon Sekiyu Kagaku Corporation, brand name: DPP-6095H

* 22: Acrylonitrile-butadiene copolymer resin, the JSR Corporation make, brand name: PNR-1H, mass average molecular weight 330,000

* 23: Product made by Sumitomo Kagaku Corporation, brand name: Bond first 7M, mass mean molecular weight 70,000

* 24: Teikoku Kagaku Sangyo Co., Ltd., SG P-3DR, mass average molecular weight 1,000,000

* 25: Styrene-butadiene copolymerization, product made in Asahi Kasei, brand name: Tough technical center M1911, mass mean molecular weight 110,000

* 26: Product made in DuPont Dow, brand name: Viton @ VTR-7119, mass average molecular weight 300,000

* 27: Product made in Nippon Polyurethane high school company, brand name: Colonate L

* 28: Product made by Shikoku Kasei Co., Ltd. 2-ethyl 4-methylimidazole (2E4MZ)

TABLE 5

Storage modulus (MPa) Bad wire bonding () Mold Flash (pcs) Tracking traces (dog) Adhesive strength (N / cm) No plasma In plasma No plasma In plasma No plasma In plasma No plasma In plasma  Example 5 5 0 0 0 0 0 0 2.35 1.96 6 One 0 0 0 0 0 0 1.47 1.57 7 0.5 0 0 0 0 0 0 0.98 0.78 8 3 0 0 0 0 0 0 2.65 2.06 9 5 0 0 0 0 0 0 2.35 1.96 10 0.5 0 0 0 0 0 0 0.49 0.39 11 0.2 0 0 0 0 0 0 0.59 0.44 Comparative example 6 6 22 0 7 0 0 25 5.88 5.10 7 2 31 0 8 8 0 29 6.86 5.98

As shown in Table 5, in the lead frame subjected to the plasma cleaning, the adhesive sheet of the present invention did not generate any poor wire bonding, mold flash, and adhesion traces. On the other hand, in the comparative example which does not contain fluorine, the number of adhesion traces was large.

Examples 12 and 13, Comparative Examples 8 and 9

In Example 12 and Comparative Examples 8 and 9, it mixed with toluene so that solid content might be 20 mass% in the composition and compounding ratio (mass part) shown in following Table 6. In Example 13, an adhesive solution was prepared by mixing methyl ethylene ketone so as to have a solid content of 20% by mass.

Next, using the obtained adhesive solution, the adhesive sheet which has an adhesive bond layer was obtained like Example 1-4, and the adhesive sheet was evaluated. The results are shown in Table 7.

In addition, in evaluation of the mold flash and adhesion trace in Table 7, it was as follows.

Mold flash

The adhesive sheets obtained in Examples 12, 13, and Comparative Examples 8 and 9 were subjected to QFN lead frames (Au-Pd-Ni-plated Cu lead frames, 4 × 16 pieces (64 in total) having an external dimension of 200 mm × 60 mm. ) And a matrix arrangement, package size of 10 mm x 10 mm, 84 pins). Subsequently, after processing for 1 hour at 175 degreeC of heat processing equivalent to a die attach in oven, the plasma cleaning process was performed. Plasma cleaning conditions were used gas: Ar, gas flow rate: 45 sccm, RF output: 450 W, processing time: 5 minutes using a plasma etching apparatus (trade name: V1000 by Yamato Chemical Co., Ltd.). Then, heat treatment equivalent to wire bonding on a hot plate was performed at 220 ° C. for 15 minutes. Next, the resin was encapsulated by a transfer mold (molding) using an epoxy mold (biphenyl epoxy clock, filler amount of 85% by mass) at a heating temperature of 180 ° C., a pressure of 10 MPa, and a treatment time of 3 minutes. 64 semiconductor devices after resin encapsulation were inspected, and the number of semiconductor devices in which the encapsulating resin adhered to the external connection portion of the lid (the surface of the adhesive sheet side of the lead) was detected as the number of mold flashes generated.

Adhesion trace

The adhesion trace was evaluated using the lead frame after evaluating a mold flash. First, the adhesive sheet was peeled from the lead frame under conditions of a peel rate of 500 mm / min. After peeling the adhesive sheet, 64 semiconductor devices were inspected, and the number of semiconductor traces in which the adhesive was adhered to the adhesive sheet peeling surface including the external connection portion of the lid and the wetted surface was defined as the number of adhered traces.

TABLE 6

Example Comparative example 12 13 8 9 Fluorine Resin Fluoroethylene vinyl ether copolymer having a functional group * 29 30 10 Fluoroethylene vinyl ether copolymer having a functional group * 30 20 Reactive elastomers Maleic anhydride-containing styrene-ethylene-butylene copolymer * 31 70 Carboxyl group-containing acrylonitrile-butadiene copolymer * 32 90 Carboxyl group-acrylonitrile-butadiene copolymer * 33 20  Etc Styrene-Butadiene Copolymer as Nonreactive Elastomer * 34 80 Phenyl resin as non-fluorine resin * 35 40 Epoxy resin as non-fluorine resin * 36 40 Hardener * 37 One One One * 38 8

* 29: Product made in Asahi Glass Company: Lumifuron LF916

* 30: Product made in Asahi Glass Company: Lumifuron LF200

* 31: The product made by Asahi Kasei Co., Ltd. Product name: Tough technical center M-1911 (maleic anhydride-containing ethylene-butylene copolymer, maleic anhydride: styrene: ethylene-butylene (mass ratio) = 0.5: 30: 70 copolymer)

* 32: Product name made in JSR company: PNR-1H

* 33: Product made in Nihon Xeon company: Nipol 1072J

* 34 made in Asahi Kasei Co., Ltd. Product name: Tough technical center H-1041

* 35: Product made in Shin-Nihon Petrochemical Co., Ltd. product name: DPP-6095H

* 36: Product made in Dainiphon Ink Kagaku Kogyo Co., Ltd. product name: HP-7200

* 37: Product made in Nippon Polyurethane high school company: Colonate L

* 38: Tokyo Kasei Corporation (2-ethyl-4-methylimidazole)

TABLE 7

Mold Flash (pcs) Adherence trace occurrence () Example 12 0 0 Example 13 0 0 Example 8 15 64 Example 9 0 No peeling off

In the resin encapsulation step for manufacturing a semiconductor device, the semiconductor element is encapsulated with a resin encapsulation by applying a pressure of 5 to 10 Gpa while heating at 150 to 200 ° C. For this reason, as a result of exposing the adhesive bond layer of an adhesive sheet to high temperature, the adhesive force (adhesive strength of an adhesive bond layer and a lead frame) of an adhesive bond falls, and an adhesive bond layer peels partially from a lead frame by the pressure of sealing resin. As a result, mold flash may occur. However, in the adhesive sheet of this invention, since the adhesive force of an adhesive bond layer does not fall so much, such a problem does not arise.

In the present invention, the generation of outgas components generated by using a silicone adhesive or the like can be suppressed, and the excellent wire bonding property and mold flash characteristics of the thermosetting adhesive when used in the manufacture of semiconductor devices such as QFN can be used. While keeping, the adhesion traces can be prevented. Thereby, the adhesive sheet for semiconductor device manufacture, a semiconductor device, and its manufacturing method which can prevent defective manufacture of a semiconductor device can be provided.

Further, even if the plasma cleaning is not performed before the wire bonding step, an adhesive sheet for semiconductor device manufacture can be provided which has good wire bonding characteristics, excellent adhesion between the lead frame and the encapsulating resin, and which can provide a highly reliable semiconductor device.

In addition, the present invention can provide an adhesive sheet for manufacturing a semiconductor device which maintains proper peelability and does not generate adhesion traces even when the adhesive layer is exposed to plasma cleaning before the wire bonding step.

Claims (16)

In the adhesive sheet for manufacturing a semiconductor device is attached to the lead frame or wiring board of the semiconductor device so as to be peeled off, A base material and an adhesive layer, The adhesive sheet contains a thermosetting resin component (a), a thermoplastic resin component (b), and a fluorine-based additive (c). The method of claim 1, The adhesive sheet for manufacturing a semiconductor device, wherein the fluorine-based additive (c) is at least one selected from the group consisting of a fluorine-containing graft polymer, a fluorine-containing block copolymer, and a fluorine-containing aliphatic polymer ester. In the adhesive sheet for manufacturing a semiconductor device is attached to the lead frame or wiring board of the semiconductor device so as to be peeled off, A base material and an adhesive layer, The adhesive sheet for manufacturing a semiconductor device, wherein the adhesive layer contains a fluororesin. The method of claim 3, wherein The adhesive layer contains a thermosetting resin component (a1) and a thermoplastic resin component (b1), wherein any one of the thermosetting resin component (a1) and the thermoplastic resin component (b1) is an olefin resin containing fluorine. Adhesive sheet for semiconductor device manufacturing. The method of claim 4, wherein The adhesive sheet for semiconductor device manufacture characterized by the mass ratio (a1) / (b1) of the thermosetting resin component (a1) and the thermoplastic resin component (b1) of the said adhesive bond layer being 0.05-0.43. The method of claim 4, wherein Adhesive sheet for manufacturing a semiconductor device, characterized in that the mass average molecular weight of the thermoplastic resin component (b1) is 2,000 to 1,000,000. The method of claim 3, wherein The storage elastic modulus after hardening of the said adhesive bond layer is 0.1 Mpa or more at 150-250 degreeC, The adhesive sheet for semiconductor device manufacture characterized by the above-mentioned. The method according to claim 1 or 3, The adhesive sheet for hardening of the said adhesive bond layer after 150-200 degreeC is 0.03-5 N / cm, The adhesive sheet for semiconductor device manufacture characterized by the above-mentioned. The method according to claim 1 or 3, An adhesive sheet for manufacturing a semiconductor device, wherein the base material is a heat resistant film having a glass transition temperature of 150 ° C. or higher and a thermal expansion coefficient of 5 to 50 ppm / ° C. The method according to claim 1 or 3, An adhesive sheet for producing a semiconductor device, wherein the base material is a metal foil having a thermal expansion coefficient of 5 to 50 ppm / ° C. In the adhesive sheet for manufacturing a semiconductor device is attached to the lead frame or wiring board of the semiconductor device so as to be peeled off, A base material and an adhesive layer, The adhesive sheet for manufacturing a semiconductor device, wherein the adhesive layer contains a fluororesin and a reactive elastomer. The method of claim 11, The adhesive sheet for producing a semiconductor device, wherein the fluororesin is a copolymer obtained by polymerizing a monomer raw material containing fluoroolefin and vinyl ether and / or a polymer obtained by polymerizing monomer raw material including fluoroolefin and vinyl ester. The method of claim 11, An adhesive sheet for producing a semiconductor device, wherein the reactive elastomer is maleic anhydride-containing styrene-ethylene-butylene copolymer. The method according to any one of claims 1, 3 and 11, Adhesive sheet for semiconductor device manufacturing, characterized in that the protective film is provided on one side of the adhesive layer. delete In manufacturing a semiconductor device using the adhesive sheet for semiconductor device manufacturing in any one of Claims 1, 3, and 11, Attaching the adhesive sheet for manufacturing the semiconductor device to one side of the lead frame, A semiconductor device is mounted on a predetermined region of the other side of the lead frame, Forming a bonding wire electrically connected to the semiconductor device and a portion of the lead frame around the semiconductor device; Forming an encapsulation resin covering the semiconductor device and the bonding wire, Peeling the adhesive sheet for manufacturing the semiconductor device from the lead frame.

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