TW201348384A - Cutting die-bonding film - Google Patents

Abstract

This invention provides a cutting/die-bonding film capable of inhibiting component transfer between a cutting film and a die-bonding film and providing an excellent semiconductor wafer holding strength during cutting and an excellent peeling property during picking. The cutting/die-bonding film of this invention comprises a first adhesive layer and a second adhesive layer, wherein the first adhesive layer comprises the polyolefin-based resin, and the second adhesive layer comprises at least one component selected from acrylic acid-based resin, epoxy-based resin and phenolic resin.

Description

Cutting/mud film

This invention relates to a dicing/mulet film.

A semiconductor wafer including germanium, gallium, or arsenic is manufactured in a large diameter state, and after patterning on the surface, the back surface is polished, and the thickness of the semiconductor wafer is usually reduced to about 100 to 600 μm, and further maintained. The film is diced and separated into semiconductor wafers (cutting step). Then, the semiconductor wafer is fixed to the adherend such as the lead frame (mounting step), and then transferred to the die bonding step. In recent years, in order to simplify the steps, reduce damage to the semiconductor wafer, and the like, an adhesive film (cut film) that holds the semiconductor wafer in the cutting step and an adhesive film (adhesive film) that fixes the semiconductor wafer in the mounting step are used. A dicing/mud film which is integrated (for example, Patent Document 1). Such a dicing/mud film generally includes a dicing film having an acrylic pressure-sensitive adhesive layer on a base film, and a viscous film disposed on the acrylic pressure-sensitive adhesive layer.

On the other hand, in order to prevent damage of the semiconductor wafer during the cutting and cutting steps in the cutting step, the dicing/mud film requires a moderate adhesive force, that is, adhesiveness (cuttable adhesion) and peelability. (adhesive peelability) adhesion. Moreover, with the thinning of semiconductor wafers in recent years, it is necessary to control the adhesion more strictly. In addition, for memory system semiconductor devices, higher quality is required on SSD (Solid State Drive). In a highly reliable package, it is necessary to improve the reliability and cleanliness of the adhesive film as a structural material.

The above dicing/mud film utilizes an acrylic adhesive layer of a dicing film to control cutting The adhesion between the film and the die film can maintain the semiconductor wafer during the cutting step, and the semiconductor wafer can be picked up after the cutting step. On the other hand, since the acrylic resin is usually contained as a material of the adhesive film, the compatibility between the adhesive layer of the dicing film and the material for forming the adhesive film is high, and various problems occur. As one of the problems, there is a problem that component transfer occurs between the dicing film/mud film, and the characteristics of the structural material as the viscous film deteriorate. Further, when the impurity layer is contained in the adhesive layer of the dicing film, the impurity ions are transferred to the viscous film, and eventually the reliability of the semiconductor device is deteriorated. Further, there is a problem that the peeling property of the dicing film to the dicing film is insufficient.

As a method for solving such a problem, an adhesive having low compatibility with an acrylic resin is used for the adhesive layer of the dicing film. However, such an adhesive is difficult to control the adhesion. A dicing/mulet film which solves the above problem of component transfer and has a moderate adhesion between the dicing film/mud film has not been realized.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-124141

The present invention has been made to solve the above problems, and an object thereof is to provide a cutting/adhesive which is excellent in suppressing component transfer between a dicing film and an adhesive film, and which is excellent in semiconductor wafer holding force and pick-up property at the time of dicing. Crystal film.

The dicing/mud film of the present invention comprises a first adhesive layer and a second adhesive layer, the first adhesive layer comprises a polyolefin resin, and the second adhesive layer comprises an acrylic resin and an epoxy resin. And at least one of phenolic resins.

In a preferred embodiment, the first adhesive layer is of a pressure sensitive type.

In a preferred embodiment, the first adhesive layer comprises amorphous propylene-(1-butyl) Alkene copolymer.

In a preferred embodiment, the first adhesive layer does not contain an acrylic resin.

In a preferred embodiment, the first adhesive layer is substantially free of F ^- , Cl ^- , Br ^- , NO ₂ ^- , NO ₃ ^- , SO ₄ ^2- , Li ⁺ , Na ⁺ , K ⁺ , Mg ^{2 +} , Ca ²⁺ and NH ₄ ⁺ .

In a preferred embodiment, the peeling force of the second adhesive layer is 0.02 N when the second adhesive layer is peeled off from the first adhesive layer under the conditions of a measurement temperature of 23 ° C, a tensile speed of 300 mm/min, and a peeling angle of 180 degrees. /20 mm~0.4 N/20 mm.

In a preferred embodiment, the dicing/mud film is further provided with a substrate layer on the side of the first adhesive layer opposite to the second adhesive layer.

In a preferred embodiment, the layered system comprising the substrate layer and the first adhesive layer is obtained by co-extrusion molding.

In another aspect of the invention, a semiconductor device is provided. This semiconductor device is manufactured using the above-described dicing/mud film.

According to the present invention, by including the polyolefin-based resin in the dicing film (first adhesive layer), it is possible to provide a semiconductor wafer holding force at the time of dicing and picking up when the component is transferred between the dicing film and the viscous film. A cleavable/mulet film excellent in peelability.

1‧‧‧First adhesive layer

2‧‧‧Second Adhesive Layer

3‧‧‧Substrate layer

100,200‧‧‧Cutting/mud film

1 is a schematic cross-sectional view of a dicing/mulet film according to a preferred embodiment of the present invention.

2 is a schematic cross-sectional view of a dicing/mulet film according to another preferred embodiment of the present invention.

3 is a schematic cross-sectional view of a semiconductor device in accordance with a preferred embodiment of the present invention.

4(a) to 4(d) are diagrams for explaining a method of manufacturing a semiconductor device.

A. The overall composition of the cutting/mud film

1 is a schematic cross-sectional view of a dicing/mulet film according to a preferred embodiment of the present invention. Cutting The adhesive film 100 includes a first adhesive layer 1 and a second adhesive layer 2 . The first adhesive layer contains a polyolefin resin, and the second adhesive layer contains at least one selected from the group consisting of an acrylic resin, an epoxy resin, and a phenol resin. The first adhesive layer 1 has a function of holding the semiconductor wafer placed on the dicing/mud film 100 in the dicing step. The second adhesive layer 2 has a function of being picked up together with the semiconductor wafer after the dicing step and fixing the semiconductor wafer to the adherend in the mounting step. In other words, the first adhesive layer constitutes a dicing film, and the second adhesive layer constitutes a viscous film.

The dicing/mud film of the present invention may not include a substrate layer (Fig. 1), and may also have a substrate layer (Fig. 2). In the embodiment of FIG. 2, the dicing/mud film 200 is further provided with a substrate layer 3 on the side of the first adhesive layer 1 opposite to the second adhesive layer 2. In the dicing/mud film 200, the first adhesive layer 1 and the substrate layer 3 constitute a dicing film 10.

The thickness of the first adhesive layer is preferably from 10 μm to 300 μm, and more preferably from 15 μm to 150 μm. When the dicing/mud film does not have a substrate layer, the thickness of the first adhesive layer is preferably 50 μm to 300 μm, more preferably 75 μm to 200 μm, and particularly preferably 75 μm to 125 μm. . In the case where the dicing/mud film has a substrate layer, the thickness of the first adhesive layer is preferably from 10 μm to 150 μm, more preferably from 15 μm to 100 μm, particularly preferably from 15 μm to 50 μm.

The thickness of the second adhesive layer is preferably from 3 μm to 200 μm, more preferably from 4 μm to 100 μm, particularly preferably from 5 μm to 80 μm.

The dicing/mud film of the present invention can be provided by a protective film. The dicing/mud film of the present invention can be wound into a roll shape in a state protected by a separator. The separator has a function as a protective dicing/mud film until it is supplied to a practical protective material. Examples of the separator include a surface-coated plastic (for example, polyethylene terephthalate (PET)) using a release agent such as a ruthenium release agent, a fluorine release agent, or a long-chain alkyl acrylate release agent. , polyethylene, polypropylene) film, non-woven fabric or paper.

At a measuring temperature of 23 ° C, a tensile speed of 300 mm / min, and a peeling angle of 180 degrees The peeling force when the second adhesive layer is peeled off from the first adhesive layer is preferably 0.02 N/20 mm to 0.4 N/20 mm, and more preferably 0.03 N/20 mm to 0.35 N/20. Mm, more preferably 0.03 N/20 mm~0.2 N/20 mm. If it is in this range, the dicing film and the viscous film can be prevented from being peeled off during the dicing step. On the other hand, when the semiconductor wafer is picked up after the dicing step, the dicing film and the viscous film are easily peeled off, and the generation of the paste residue can be prevented. .

B. Cutting film

The dicing film in the dicing/mud film of the present invention is provided with a first adhesive layer. As described above, the dicing film may be provided with a base material layer or may not include a base material layer.

B-1. First adhesive layer

The first adhesive layer contains a polyolefin resin. When the first adhesive layer formed of a polyolefin resin is provided, component transfer between the first adhesive layer and the second adhesive layer (mud film) is suppressed. As a result, it is possible to prevent deterioration of characteristics of the structural material as the adhesive film. In addition, when a polyolefin-based resin is used, a first adhesive layer having a high strength can be obtained. Therefore, a dicing/mulet film excellent in handleability can be obtained without providing a base material layer. The first adhesive layer is preferably of a pressure sensitive type. In the case of a pressure sensitive type, a dicing/mulet film which can simplify the manufacturing steps of the semiconductor device can be obtained.

As the polyolefin-based resin, any suitable polyolefin-based resin can be used as long as it is a polyolefin-based resin that exhibits adhesiveness. Examples of the polyolefin-based resin that exhibits adhesiveness include amorphous polypropylene, amorphous propylene-ethylene copolymer, amorphous propylene-(1-butene) copolymer, and amorphous propylene-ethylene- Butene copolymer and the like. Among them, an amorphous propylene-(1-butene) copolymer is preferred. In the present specification, "amorphous" means a property which does not have a clear melting point such as crystallinity.

The above amorphous propylene-(1-butene) copolymer is preferably obtained by polymerizing propylene with 1-butene using a metallocene catalyst. Such an amorphous propylene-(1-butene) copolymer can be obtained, for example, by carrying out a polymerization step of polymerizing propylene and 1-butene using a metallocene catalyst, After the polymerization step, a post-treatment step such as a residual catalyst removal step or a foreign matter removal step is performed. The amorphous propylene-(1-butene) copolymer is obtained by such a step, for example, in the form of a powder, a pellet or the like. Examples of the metallocene catalyst include a metallocene-supporting catalyst obtained by uniformly mixing a metallocene compound with a metallocene of aluminoxane and a metallocene compound supported on a particulate carrier.

The content ratio of the constituent unit derived from propylene in the amorphous propylene-(1-butene) copolymer is preferably from 80 mol% to 99 mol%, more preferably from 85 mol% to 99 mol%. %, particularly preferably 90% by mole to 99% by mole.

The content ratio of the constituent unit derived from 1-butene in the amorphous propylene-(1-butene) copolymer is preferably from 1 mol% to 15 mol%, more preferably 1 mol%. 10 moles %. In such a range, it is possible to obtain a dicing film having an appropriate adhesion to the die-bonding film (second adhesive layer), and the holding force at the time of the dicing step and the peeling property at the time of picking up.

The above amorphous propylene-(1-butene) copolymer may be a block copolymer or a random copolymer.

The amorphous propylene-(1-butene) copolymer may also contain constituent units derived from other monomers within the range which does not impair the effects of the present invention. Examples of the other monomer include ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene. And other alpha-olefins.

The amorphous propylene-(1-butene) copolymer polymerized using the metallocene catalyst as described above exhibits a narrow molecular weight distribution. Specifically, the amorphous propylene-(1-butene) copolymer has a molecular weight distribution (Mw/Mn) of 2 or less, preferably 1.1 to 2, and more preferably 1.2 to 1.9. When such an amorphous propylene-(1-butene) copolymer exhibiting a narrow molecular weight distribution is used, it is possible to prevent bleeding of a low molecular weight component.

The amorphous propylene-(1-butene) copolymer has a weight average molecular weight (Mw) of 200,000 or more, preferably 200,000 to 500,000, and more preferably 200,000~. 300,000. When the weight average molecular weight (Mw) of the amorphous propylene-(1-butene) copolymer is in this range, appropriate adhesion can be obtained, and bleeding of low molecular weight components can be prevented. Further, when the first adhesive layer and the base material layer are co-extruded, the first adhesive layer can be formed without processing defects.

The melt flow rate of the amorphous propylene-(1-butene) copolymer at 230 ° C and 2.16 kgf is preferably from 1 g/10 min to 50 g/10 min, and further preferably 5 g/10 min. ~30 g/10 min, particularly preferably 5 g/10 min~20 g/10 min. If the melt flow rate of the amorphous propylene-(1-butene) copolymer is in such a range, when the first adhesive layer and the substrate layer are co-extruded, a first adhesive having a uniform thickness can be formed. The layer is not processed. The melt flow rate can be determined by the method according to JIS K7210.

As the polyolefin-based resin, the above-mentioned polyolefin-based resin which exhibits adhesiveness and the crystalline polypropylene-based resin can be used in combination. By including the crystalline polypropylene-based resin in the first adhesive layer, the adhesion of the first adhesive layer can be reduced, and the dicing film excellent in the holding force at the time of the dicing step and the peeling property at the time of pick-up can be obtained. In addition, by including a crystalline polypropylene-based resin, the storage modulus of the first adhesive layer can be increased, and a dicing/mulet film excellent in handleability can be obtained. Such a dicing/mud film is excellent in workability even if it does not have a base material layer. The content of the crystalline polypropylene resin is preferably from 0% by weight to 90% by weight, more preferably from 0% by weight to 90% by weight based on the total weight of the polyolefin resin and the crystalline polypropylene resin which exhibits the adhesiveness. 20% by weight to 90% by weight, particularly preferably 40% by weight to 90% by weight.

The above crystalline polypropylene-based resin may be a homopolypropylene or a copolymer obtained by a propylene and a monomer copolymerizable with propylene. Examples of the monomer copolymerizable with propylene include ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl- An α-olefin such as 1-pentene or the like.

The crystalline polypropylene-based resin is preferably obtained by polymerization using a metallocene catalyst in the same manner as the above amorphous propylene-(1-butene) copolymer. If you use the method to get the knot The crystalline polypropylene resin can prevent bleeding of low molecular weight components.

The crystallinity of the crystalline polypropylene-based resin is preferably 10% or more, and more preferably 20% or more. The degree of crystallinity is typically determined by differential scanning calorimetry (DSC) or X-ray diffraction.

The above first adhesive layer may contain other components within the scope of the effects of the present invention. Examples of the other component include an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antistatic agent. The type and amount of other ingredients can be appropriately selected according to the target.

The first adhesive layer preferably contains no acrylic resin, and further preferably does not contain an acrylic resin, an epoxy resin, or a phenol resin, and particularly preferably contains no acrylic resin, epoxy resin, or phenol. A resin and a compound having high compatibility with the resins. This is because the component transfer between the first adhesive layer (cut film) and the second adhesive layer (mud film) can be suppressed. According to the present invention, a dicing film having a moderate adhesiveness can be obtained even without such compounds.

Preferably, the first adhesive layer is substantially free of F ^- , Cl ^- , Br ^- , NO ₂ ^- , NO ₃ ^- , SO ₄ ^2- , Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ and NH ₄ ⁺ . The first adhesive layer which does not substantially contain the above-mentioned ions can be formed, for example, as a polyolefin-based resin constituting the first adhesive layer, and a polyolefin-based resin obtained by solution polymerization using a metallocene catalyst ( For example, the above amorphous propylene-(1-butene) copolymer and the above crystalline polypropylene-based resin). In the solution polymerization using the metallocene catalyst, the polyolefin resin can be purified by repeating precipitation separation (reprecipitation method) using a poor solvent different from the polymerization solvent, so that the first adhesive containing no such ions can be obtained. Floor. Furthermore, in the present specification, "substantially free of F ^- , Cl ^- , Br ^- , NO ₂ ^- , NO ₃ ^- , SO ₄ ^2- , Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ^{2 "+} , NH ₄ ⁺ " means that the limit is not reached in standard ion chromatography (for example, ion chromatographic analysis using the trade names "DX-320" and "DX-500" manufactured by Dionex Corporation). Specifically, it means that F ^- , Cl ^- , Br ^- , NO ₂ ^- , NO ₃ ^- , SO ₄ ^2- and K ⁺ are respectively 0.49 μg or less with respect to 1 g of the first adhesive layer, Li ⁺ and The Na ⁺ is 0.20 μg or less, the Mg ²⁺ and Ca ²⁺ are 0.97 μg or less, and the NH ₄ ⁺ is 0.5 μg or less.

The storage modulus (G') of the first adhesive layer at 20 ° C is preferably from 0.5 × 10 ⁶ Pa to 1.0 × 10 ⁸ Pa, more preferably from 0.8 × 10 ⁶ Pa to 3.0 × 10 ⁷ Pa. The dicing/mud film of the present invention is capable of obtaining a storage modulus (G') having such a range, and having a moderate adhesion to the viscous film (second adhesive layer), and retention during the cutting step and A dicing film excellent in peelability at the time of picking up. When the storage modulus (G') of the first adhesive layer is in the above range, a dicing/mulet film excellent in peeling resistance can be obtained. In addition, a dicing/mulet film excellent in handleability can be obtained. Further, even when the semiconductor wafer has irregularities on the surface, a dicing/mulet film which can follow the irregularities can be obtained. If such a dicing/mud film is used, contamination of the semiconductor wafer caused by the cutting water can be prevented in the cutting step. Among them, the storage modulus (G') can be determined by dynamic viscoelastic spectroscopy.

B-2. Substrate layer

As the material constituting the above substrate layer, any appropriate material can be employed. Examples of the material constituting the substrate layer include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, and block copolymer polypropylene. Polyolefins such as homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) polyesters such as copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, polyurethanes, polyethylene terephthalate, polyethylene naphthalate, etc. Polycarbonate, polyimidazole, polyetheretherketone, polyimide, polyetherimine, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aromatic polyamine (paper), Glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, fluorenone resin, metal (foil), paper, and the like. When the dicing film provided with the base material layer is produced by co-extrusion molding, a thermoplastic resin is selected as a material constituting the base material layer. Among them, an ethylene-vinyl acetate copolymer is preferred.

The weight average molecular weight (Mw) of the above ethylene-vinyl acetate copolymer is preferably from 10,000 to 200,000, more preferably from 30,000 to 190,000. When the weight average molecular weight (Mw) of the ethylene-vinyl acetate copolymer is in such a range, the base material layer can be formed by co-extrusion molding without processing failure.

The ethylene-vinyl acetate copolymer preferably has a melt flow rate of 2 g/10 min to 20 g/10 min at 190 ° C and 2.16 kgf, and more preferably 5 g/10 min to 15 g/10 min. It is particularly preferably 7 g/10 min to 12 g/10 min. When the melt flow rate of the ethylene-vinyl acetate copolymer is in this range, the base material layer can be formed by co-extrusion molding without processing defects.

The above-mentioned base material layer may contain other components within the range which does not impair the effects of the present invention. As the other component, for example, the same components as those of the other components which can be included in the first adhesive layer described in the above item B-1 can be used.

B-3. Method for manufacturing dicing film

The above dicing film can be formed by any suitable forming method. Preferably, the dicing film is formed by extrusion molding. In the case where the dicing film is provided with the base material layer, the dicing film is preferably formed by co-extrusion molding. According to the co-extrusion molding, it is possible to produce a dicing adhesive sheet having good adhesion between layers with a small number of steps and without using an organic solvent.

In the above coextrusion molding, a material for forming the first adhesive layer and the base material layer may be a material obtained by mixing the components of the respective layers by any appropriate method.

As a specific method of the above-described co-extrusion molding, for example, a method of supplying a first adhesive layer forming material to one unit and supplying another material to at least two extruders connected to a dies is exemplified. The material forming material is melted, extruded, and taken out by a contact roll forming method to form a laminate. At the time of extrusion, the closer the portions where the forming materials are joined, the closer the mold outlet (mould) is. This is because the merging failure of each of the forming materials is less likely to occur in the mold. Therefore, as the above mold, it is preferable to use a multi-manifold form Mold. Further, in the case where the merging failure occurs, appearance defects such as merging unevenness occur, and specifically, the wavy appearance between the extruded first adhesive layer and the substrate layer is uneven, which is not preferable. In addition, the merging failure occurs because, for example, the difference in fluidity (melt viscosity) of the different kinds of forming materials in the mold is large, and the difference in the shearing speed of the forming materials of the respective layers is large, and therefore, if a multi-manifold form is used, For molds, the range of material selection is expanded for different types of forming materials having differences in fluidity compared to other forms (for example, in the form of a feed block). The screw type for the extruder for melting each of the formed materials may be a single screw or a double screw. The extruder can also be three or more. When the number of extruders is three or more, the material for forming the other layers can be further supplied. In the case where an adhesive tape having a two-layer structure (base material layer + first adhesive layer) is produced by using three or more extruders, the same forming material is supplied to two or more adjacent extruders. For example, when three extruders are used, the same forming material can be supplied to two adjacent extruders.

The molding temperature in the above coextrusion molding is preferably from 160 ° C to 220 ° C, more preferably from 170 ° C to 200 ° C. When it is such a range, it is excellent in shaping|molding stability.

The difference between the first adhesive layer forming material and the shearing viscosity of the substrate layer forming material at a temperature of 180 ° C and a shear rate of 100 sec ^-1 (adhesive forming material - base material forming material) is preferably -150 Pa. s~600 Pa. s, and further preferably -100 Pa. s~550 Pa. s, particularly preferably -50 Pa. s~500 Pa. s. In such a range, the fluidity of the adhesive forming material and the base layer forming material in the mold is similar, and the occurrence of merging failure can be prevented. Further, the shear viscosity can be measured by a double capillary type elongational viscometer.

C. Muc film

The die bond film in the dicing/mud film of the present invention is provided with a second adhesive layer. The adhesive film may be formed of, for example, a single layer of an adhesive layer (second adhesive layer), or may have a multilayer structure in which a second adhesive layer is formed on both surfaces of the core material. As the above core material, for example Examples thereof 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 fiber or a plastic film. A fiber-reinforced resin substrate, a ruthenium substrate, a glass substrate, or the like.

The second adhesive layer contains an acrylic resin, an epoxy resin, or a phenol resin. These resins have a small content of impurity ions and are excellent in heat resistance. These resins may be used singly or in combination of two or more.

Any suitable acrylic resin can be used as the acrylic resin. The acrylic resin may, for example, be one containing an ester of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of preferably 30 or less, more preferably 4 to 18, or A polymer obtained by polymerizing two or more kinds of monomer components.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group or a cyclohexyl group. , 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, Octadecyl, dodecyl and the like.

Any other monomer may be contained in the monomer component forming the acrylic resin. Examples of the other monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, methylene succinic acid, maleic acid, fumaric acid, crotonic acid, and the like. a monomer of a carboxyl group; an anhydride monomer such as maleic anhydride or methylene succinic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid 4 -hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, acrylic acid a hydroxyl group-containing monomer such as -(4-hydroxymethylcyclohexyl)methyl ester; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, (A) a sulfonic acid group-containing monomer such as acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid, or the like; 2-hydroxyethyl acryl thiophosphate a phosphate group monomer or the like.

The glass transition temperature (Tg) of the acrylic resin is preferably from -30 ° C to 30 ° C, more preferably from -20 ° C to 15 ° C.

The content ratio of the acrylic resin in the second adhesive layer is preferably from 30% by weight to 95% by weight, and more preferably from 50% by weight to 90% by weight.

As the epoxy resin, any suitable epoxy resin can be used as long as it is an epoxy resin which is generally used as an adhesive composition. Examples of the epoxy resin include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, and the like. Bismuth type, phenol novolac type, o-cresol novolak type, trihydroxyphenylmethane type, tetraphenol ethyl ethane type and other difunctional epoxy resin, polyfunctional epoxy resin; Resin; triglycidyl isocyanurate type epoxy resin; glycidylamine type epoxy resin. Among them, a novolak type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type epoxy resin or a tetraphenol ethane type epoxy resin is preferable. This is because it is excellent in hardenability and heat resistance. These resins may be used singly or in combination of two or more.

Examples of the phenolic resin include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a novolak phenol novolak resin; A cresol type phenol resin; polyoxy styrene such as polyparaoxy styrene or the like. Among them, a phenol novolak resin and a phenol aralkyl resin are preferable. The reason for this is that the connection reliability of the semiconductor device manufactured using the dicing/mud film of the present invention can be improved. The phenol resin acts as a curing agent for the epoxy resin.

When the epoxy resin and the phenol resin are used in combination, the blending ratio of the epoxy resin to the phenol resin is preferably 1 part by weight based on the epoxy group in the epoxy resin component. The hydroxyl group is formulated in a form of from 0.5 equivalent to 2.0 equivalents, more preferably from 0.8 equivalents to 1.2 equivalents. When the blending ratio of the epoxy resin and the phenol resin deviates from the above range, the curing reaction is not performed sufficiently, and the epoxy resin cured product is not provided. The characteristics are prone to deterioration. The total content of the epoxy resin and the phenol resin in the second adhesive layer is preferably 5% by weight to 80% by weight, and more preferably 10% by weight to 70% by weight.

The second adhesive layer may also contain other thermoplastic resins and/or thermosetting resins. Examples of the other thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and poly Butadiene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon, 6,6-nylon and other polyamide resin, phenoxy resin, acrylic resin, PET, PBT and other saturated polyester resins, Polyamidoximine resin, fluororesin, and the like. Examples of the other thermosetting resin include an amine resin, an unsaturated polyester resin, a polyurethane resin, an anthrone resin, and a thermosetting polyimide resin. These resins may be used singly or in combination of two or more.

The second adhesive layer may be added with a polyfunctional compound capable of reacting with a functional group or the like at the end of the molecular chain of the resin contained in the second adhesive layer as a crosslinking agent. By adding such a polyfunctional compound, it is possible to improve the adhesion characteristics at a high temperature and to improve the heat resistance. Examples of the polyfunctional compound include polyisocyanate such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and an adduct of a polyhydric alcohol and a diisocyanate. The content ratio of the polyfunctional compound is preferably from 0.05% by weight to 0.7% by weight based on the total amount of the resin. These polyfunctional compounds may be used singly or in combination of two or more.

The second adhesive layer may also contain an inorganic filler. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and nitrogen. Boron, crystalline cerium oxide, amorphous cerium oxide, clay, gypsum, etc. Further, the second adhesive layer may contain a conductive inorganic filler in order to impart conductivity, improve thermal conductivity, and the like. Examples of the conductive inorganic filler include silver, aluminum, gold, copper, nickel, and conductivity. Metal oxides such as alloys and alumina, amorphous carbon black, graphite, and the like. The content ratio of the inorganic filler is preferably 80% by weight or less, and more preferably 70% by weight or less based on the total amount of the resin. The average particle diameter of the inorganic filler is preferably from 0.1 μm to 80 μm.

The second adhesive layer may also contain any suitable other additives as needed. Examples of other additives include a flame retardant, a decane coupling agent, and an ion scavenger. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. Examples of the decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropyl group. Diethoxy decane and the like. Examples of the ion scavenger include hydrotalcites and barium hydroxide.

The shearing force of the adhesive film before bonding the adhesive film to the first adhesive layer of the dicing film as described later on the BGA substrate at 175 ° C is preferably 0.05 MPa or more, and further preferably 0.07. Above MPa, it is particularly preferably 0.1 MPa to 1 MPa. Here, the shearing force is measured by the method described later.

The adhesion of the adhesive film to the BGA substrate at 175 ° C when the surface in contact with the dicing film of the dicing film removed from the dicing/mud film of the present invention is attached to the BGA substrate, The shearing force of the adhesive film before bonding the adhesive film to the first adhesive layer of the dicing film to the BGA substrate is preferably 80% or more, more preferably 95% or more, and particularly preferably 100%. Above, the best is 100% to 120%. Since the dicing/mud film of the present invention is suppressed from being transferred by a component between the dicing film and the viscous film, it is possible to prevent the adhesion of the wick film from being lowered. Here, the shearing force is measured by the method described later.

D. Cutting/mud film manufacturing method

The dicing/mulet film of the present invention is obtained by providing a viscous film on the first adhesive layer having the first adhesive layer and the dicing film of any of the substrate layers.

The dicing film can be obtained by the method described in the above item B-3. On the other hand, the adhesive film can apply the adhesive film forming material (second adhesive layer forming material) to the release paper. It is obtained by drying. The adhesive film obtained in this manner is transferred onto the first adhesive layer of the dicing film, whereby a dicing/mulet film can be obtained. Further, the die bond film may be obtained by applying a second adhesive layer forming material to the core material described in the above item C, followed by drying. In this case, the second adhesive layer and the core material constitute a die-bonding film, and the second adhesive layer of the adhesive film is bonded to the first adhesive layer of the dicing film, thereby obtaining a dicing/mud film. .

Alternatively, the dicing/mulet film can also be obtained by directly applying the adhesive film forming material (second adhesive layer forming material) onto the first adhesive layer of the dicing film and then drying.

E. Semiconductor device

3 is a schematic cross-sectional view of a semiconductor device in accordance with a preferred embodiment of the present invention. The semiconductor device 300 is manufactured using the dicing/mud film of the present invention. In the semiconductor device 300, the semiconductor wafer 41 is then fixed to the substrate or the lead frame (hereinafter collectively referred to as the adherend 30) via the die-bonding film 2 (the second adhesive layer 2 of the dicing/mud film). Further, the electrode terminal of the semiconductor wafer 41 and the electrode pad of the semiconductor wafer 41 are electrically connected to each other by the bonding wire 50 at the front end of the terminal portion (internal lead) of the adherend 30. The semiconductor wafer 41 is sealed by a sealing resin 60. The semiconductor device 300 manufactured by using the dicing/mud film of the present invention has less resin component and impurity ions transferred from the dicing film (first adhesive layer) in the viscous film 2, thereby being clean, reliable, and durable. Excellent sex.

FIG. 4 is a view for explaining a method of manufacturing the semiconductor device 300. At the time of manufacture of the semiconductor device 300, first, the thickness-adjusted semiconductor wafer 40 is pressure-bonded to the die-bonding film 2 (second adhesive layer 2) of the dicing/mud film 100, and then held and fixed. Further, as shown in FIG. 4(a), the semiconductor wafer 40 is diced, and the semiconductor wafer is diced and individualized to form a semiconductor wafer 41 (cutting step). Further, as shown in FIG. 4(b), the semiconductor wafer 41 attached to the dicing die-bonding film 100 is picked up. At this time, the semiconductor wafer 41 is picked up together with the die film (second adhesive layer 2). As a method of picking up, any suitable method can be employed. As a method of picking up, for example, a needle can be cited (needle) A method of picking up the semiconductor wafer 41 from the side of the dicing/mud film 100, picking up the semiconductor wafer 41 lifted up by a pick-up device, or the like. Then, as shown in FIG. 4(c), the picked-up semiconductor wafer 41 is then fixed to the adherend 30 via the die-bonding film (second adhesive layer 2) (bonding step). Then, as shown in FIG. 4(d), wire bonding is performed by electrically connecting the front end of the terminal portion (internal lead) of the adherend 30 to the electrode pad on the semiconductor wafer 41 by the bonding wire 50 (wire bonding step). . Then, the semiconductor wafer is sealed with a sealing resin 60, and the sealing resin 60 is post-cured. The semiconductor device 300 is fabricated by the above method.

As the substrate, any suitable substrate can be employed. Examples of the lead frame include a metal lead frame such as a Cu lead frame and a 42 Alloy lead frame, and examples thereof include an organic substrate containing glass epoxy, BT (bismaleimide-triazine), and polyimine.

Examples of the bonding wire 50 include a gold wire, an aluminum wire, and a copper wire.

An example of the sealing resin 60 is an epoxy resin.

The present invention is specifically described below based on examples, but the present invention is not limited by the examples. Further, in the examples, "parts" and "%" are based on weight unless otherwise specified.

[Manufacturing Example 1] Production of an adhesive film

667 parts (solid content: 100%) of an acrylic resin (manufactured by Nagase Chemtex Co., Ltd., product name: "SG-P3", solid content: 15%), and an epoxy resin (manufactured by JER Co., Ltd., trade name "Epikote 1004"), 10.8 parts 14.2 parts of phenol resin (manufactured by Mitsui Chemicals, Inc., trade name "MILEX XLC-4L") and 67.3 parts of cerium oxide filler (manufactured by Admatechs Co., Ltd., trade name "SO-25R") were dissolved in methyl ethyl ketone. A film forming material having a concentration of 23.6% by weight was prepared.

The adhesive film forming material was applied onto a polyethylene terephthalate film (thickness: 50 μm) subjected to an oxime release treatment, and then dried at 130 ° C for 2 minutes to obtain a die-crystal having a thickness of 25 μm. membrane.

[Example 1]

As the first adhesive layer forming material, a crystalline polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., trade name "WINTEC WFX4", Mw = 363,000, Mw/Mn = 2.87) 80 was used. Amorphous propylene-(1-butene) copolymer polymerized by a metallocene catalyst (manufactured by Sumitomo Chemical Co., Ltd., trade name "Tafthren H5002": constituent unit derived from propylene 90% by volume/source A mixture of 10 parts per mole of 1-butene, Mw = 230,000, Mw / Mn = 1.8) 20 parts.

As the base layer forming material, an ethylene-vinyl acetate copolymer (EVA) (manufactured by Mitsui DuPont, trade name "EVAFLEX P-1007") was used.

The adhesive layer forming material and the base layer forming material were respectively placed in an extruder, and subjected to T-die melt co-extrusion (extruder: GM ENGINEERING, trade name "GM30-28" / T-die: The module module method; extrusion temperature: 180 ° C), a dicing film having a thickness of the first adhesive layer of 45 μm and a thickness of the substrate layer of 85 μm was obtained. Furthermore, the thickness of each layer is controlled by the shape of the T-die exit.

The adhesive film obtained in Production Example 1 was attached to the side of the first adhesive layer of the obtained dicing film at room temperature to prepare a dicing/mud film (substrate layer/first adhesive layer/second adhesive layer) Agent layer (mud film)).

[Embodiment 2]

As the first adhesive layer forming material, a crystalline polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., trade name "WINTEC WFX4", Mw = 363,000, Mw/Mn = 2.87) 40 was used. Amorphous propylene-(1-butene) copolymer polymerized by a metallocene catalyst (manufactured by Sumitomo Chemical Co., Ltd., trade name "Tafthren H5002": constituent unit derived from propylene 90% by volume/source A dicing/mulet film was produced in the same manner as in Example 1 except that a mixture of 10-molecular constituent unit 10 mol%, Mw = 230,000, and Mw/Mn = 1.8) was used.

[Example 3]

As the first adhesive layer forming material, a crystalline polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., trade name "WINTEC WFX4", Mw = 363,000, Mw/Mn = 2.87) 20 was used. Amorphous propylene-(1-butene) copolymer polymerized by a metallocene catalyst (manufactured by Sumitomo Chemical Co., Ltd., trade name "Tafthren H5002": constituent unit derived from propylene 90% by volume/source A dicing/mulet film was produced in the same manner as in Example 1 except that a mixture of 10-molecular constituent unit 10 mol%, Mw = 230,000, and Mw/Mn = 1.8) was used.

[Comparative Example 1]

100 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl acrylate, 0.2 parts of benzoyl peroxide and 60 parts were placed in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device. Toluene was subjected to polymerization treatment at 62 ° C for 8 hours in a nitrogen gas stream to obtain an acrylic resin having a weight average molecular weight of 800,000 (Mw = 80,000, Mw / Mn = 6.7).

Then, 5 parts of the obtained acrylic resin was added with 5 parts of a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name "CORONATE L"), and the mixture was stirred while diluting with ethyl acetate to prepare a uniform resin solution.

The obtained resin solution was applied onto an anthrone-treated surface of an anthrone-treated PET release liner, and heat-crosslinked at 120 ° C for 2 minutes to obtain an adhesive layer having a thickness of 45 μm.

The obtained adhesive layer was transferred onto an ethylene-vinyl acetate copolymer (EVA) film to obtain a first adhesive layer (acrylic resin, thickness: 45 μm) and a substrate layer (EVA, thickness: 85). Μm) of the cutting film. Further, an ethylene-vinyl acetate copolymer (EVA) film was obtained by extrusion molding a trade name "EVAFLEX P-1007" manufactured by Mitsui DuPont.

The adhesive film obtained in Production Example 1 was attached to the side of the first adhesive layer of the obtained dicing film at room temperature to prepare a dicing/mud film (substrate layer/first adhesive layer/second adhesive layer) Agent layer (mud film)).

[Comparative Example 2]

The first adhesive layer forming material was obtained in the same manner as in Example 1 except that a thermoplastic acrylic resin (trade name "LA2140e": Mw = 74,000, Mw/Mn = 1.3) was used. Cutting/mud film.

[Evaluation]

The dicing/mulet film produced in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Table 1.

(1) Adhesion between the film-cut film (between the first adhesive layer and the second adhesive layer)

The cut/mold film was cut into 100 mm × 100 mm. Then, the tape (manufactured by Nitto Denko Corporation, trade name "BT-315") was attached to the second adhesive layer at room temperature to enhance the second adhesive layer. Then, the first adhesive layer and the second adhesive layer were sandwiched, and a tensile tester (manufactured by Shimadzu Corporation, trade name "AGS-J") was used, and the measurement temperature was 23 ° C, and the peeling speed was 300 mm / The peeling force when the second adhesive layer was peeled off from the first adhesive layer was measured under the condition of a peel angle of 180°. Then, the obtained value was divided by 5 to calculate the peeling force in a width of 20 mm. It is used as the adhesion between the film and the film.

(2) Chip fly when cutting

The produced dicing/adhesive film was pressure-bonded to a Si mirror wafer (diameter 12 cm) at 40 ° C (stage temperature). Then, the cutting is performed. The Si mirror wafer was completely cut by cutting to a wafer size of 10 mm square. The wafer flying at the time of dicing was evaluated by the ratio of the number of wafers flying in the dicing to the total number of wafers after dicing. The case where all the wafers are not flying is set to ○, and the case where one or more wafers are flying is set to ×.

Further, as a Si mirror wafer for dicing, a wafer having a thickness of 0.6 mm was back-polished using a trade name "DGP8760" manufactured by DISCO Corporation to obtain a Si mirror wafer having a thickness of 300 μm. In addition, the details of the fitting conditions and cutting conditions are as follows As described below.

(fit condition)

Attachment device: manufactured by Nitto Seiki Co., Ltd., trade name "MA-3000II"

Attached speedometer: 10 mm/min

Attachment pressure: 0.15 MPa

Stage temperature at the time of attachment: 40 ° C

(cutting conditions)

Cutting device: "DFD-6361" manufactured by DISCO

Cutting method: step cutting

Cutting ring: manufactured by DISCO, trade name "2-12-1"

Cutting speed: 30 mm/sec

Cutting blade Z1: manufactured by DISCO, under the trade name "NBC-ZH203O-SE27HCDD"

Cutting blade Z1 speed: 40,000 rpm

Blade Z1 height: one half of the height (thickness) of the Si mirror wafer

Cutting blade Z2: manufactured by DISCO, trade name "NBC-ZH103O-SE27HCBB"

Cutting blade Z2 speed: 45,000 rpm

Blade Z2 height: the center of the thickness direction of the first adhesive layer

Wafer wafer size: 10.0 mm square

(3) Pickup

After the dicing was carried out as evaluated in the above (2), the adhesive film (second adhesive layer) and the laminate of the wafer were picked up from the dicing film (first adhesive layer) under the following conditions.

Furthermore, as a Si mirror wafer (diameter 12 cm), in addition to a Si mirror wafer having a thickness of 300 μm, a Si mirror wafer having a thickness of 50 μm was used, and the wafer thicknesses of 300 μm and 50 μm were evaluated by the following criteria. Pickability of both wafers.

◎... wafers with a thickness of 300 μm and wafers of 50 μm have a pick-up height of less than 600 μm

○...The wafer pick-up height of the wafer with a thickness of 300 μm is less than 600 μm, and the pick-up height of the wafer with a thickness of 50 μm is 600 μm or more or cannot be picked up.

×...The wafer with a thickness of 300 μm and the 50 μm wafer have a pick-up height of 600 μm or more or cannot be picked up.

(pick condition)

Pickup device: manufactured by Shinkawa Co., Ltd., trade name "SPA-300"

Number of needles: 5

Needle type: F0.7, 15°, 101, 350 μm

Picking speed: 5 mm/sec

Pick up time: 1000 msec

(4) Adhesive film (second adhesive layer) - adhesion between substrates

The self-made dicing/mud film peeling film (second adhesive layer). The surface of the adhesive film which was not in contact with the dicing film (first adhesive layer) was attached to a semiconductor element (10 mm × 10 mm × 0.5 mm, material: Si) in an atmosphere of 40 ° C. Further, the semiconductor element was mounted on a BGA substrate (manufactured by JAPAN CIRCUIT Co., Ltd., trade name "CA BGA 4") via the die-bonding film (attachment conditions; temperature: 120 ° C, pressure: 0.1 MPa, time: 1 second) . Then, the die bond film (second adhesive layer) at 175 ° C and 500 μm/sec was measured by a die bond tester (Bond Tester; manufactured by Dage, trade name "dagy4000"). .

On the other hand, the shear adhesion force was measured in the same manner as described above using the adhesive film produced in Production Example 1 (i.e., the adhesive film having no history of contact with the dicing film). The shear bond strength of the adhesive film produced in Production Example 1 was 0.07 MPa.

The interpenetrating film-substrate between the dicing/mud film produced in the examples and the comparative examples was evaluated using the shear adhesion force of the adhesive film produced in Production Example 1 as 0.07 MPa as a standard. force. In other words, the case where the adhesion between the die-substrate and the substrate is 0.07 MPa or more is ○, and the case where the adhesion is less than 0.07 MPa is ×.

(5) voids in the die film (second adhesive layer)

The die-attached wafer obtained in the above (3) was mounted on a BGA substrate using a die bonder (Die Bonder; manufactured by Shinkawa Co., Ltd., trade name "SPA-300") (attachment conditions; temperature: 160 ° C, Pressure: 0.2 MPa, time: 2 seconds). Then, it was heated at 175 ° C for 1 hour, and further sealed with a sealing material (manufactured by Nitto Denko Corporation, trade name "GE-100") to manufacture a semiconductor device (TFBGA package 16 mm × 16 mm × 0.7 mm, wafer) Size 5 × 5 mm).

The semiconductor device was cut in the thickness direction with a glass knife, and the cut surface was observed with a microscope to measure the area of the void. The measurement of the void area is performed on the cut faces of the five randomly selected positions. The case where the average value of the five positions of the ratio of the void area to the cut surface is less than 3 area% is ○, and the case where the area is 3 area% or more is ×.

It is clear from Table 1 that the viscous film-cut film of the dicing/mud film of the present invention has a viscosity The force is appropriately controlled, and the semiconductor wafer holding force at the time of cutting and the peeling property at the time of picking are excellent. Further, the adhesive film which is peeled off from the dicing/mud film of the present invention is excellent in adhesion to the substrate, and is excellent in reliability when the semiconductor wafer is packaged. Further, the occurrence of voids in the adhesive film at the time of encapsulation can be suppressed, and the trouble in the subsequent reflow step can be prevented.

The dicing/mulet film of the present invention contains a polyolefin-based resin because the dicing film (first adhesive layer) inhibits component transfer between the dicing film and the viscous film, and thus, as described above, the cutting according to the present invention/ The adhesion film of the die-peeled film is excellent in adhesion, and also suppresses generation of voids.

1‧‧‧First adhesive layer

2‧‧‧Second Adhesive Layer

100‧‧‧Cutting/mud film

Claims (9)

A dicing/mud film comprising a first adhesive layer and a second adhesive layer, the first adhesive layer comprising a polyolefin resin, the second adhesive layer comprising an acrylic resin, an epoxy resin And at least one of phenolic resins. The dicing/mulet film of claim 1, wherein the first adhesive layer is of a pressure sensitive type. The dicing/mulet film of claim 1, wherein the first adhesive layer comprises an amorphous propylene-(1-butene) copolymer. The dicing/mulet film of any one of claims 1 to 3, wherein the first adhesive layer is free of an acrylic resin. The dicing/mud film according to any one of claims 1 to 3, wherein the first adhesive layer is substantially free of F ^- , Cl ^- , Br ^- , NO ₂ ^- , NO ₃ ^- , SO ₄ ^2- , Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ and NH ₄ ⁺ . The dicing/mud film according to any one of claims 1 to 3, wherein the first adhesive layer is peeled off from the first adhesive layer at a measurement temperature of 23 ° C, a tensile speed of 300 mm/min, and a peeling angle of 180 degrees. The peel force of the second adhesive layer is 0.02 N/20 mm~0.4 N/20 mm. The dicing/mulet film according to any one of claims 1 to 3, further comprising a substrate layer on a side of the first adhesive layer opposite to the second adhesive layer. The dicing/mulet film of claim 7, wherein the layered system comprising the above-mentioned substrate layer and the first adhesive layer is obtained by co-extrusion molding. A semiconductor device manufactured using the dicing/mulet film of claim 1.