TW202100690A - Dicing and die attach film including a dicing tape and an adhesive layer - Google Patents

Abstract

The present invention provides a dicing and die attach film, which is less prone to float between an adhesive layer and an adhering layer during cold expansion and normal temperature expansion, and thereafter. The present invention is a dicing and die attach film, which includes: a dicing tape, which has a laminated structure including a substrate and an adhering layer; and an adhesive layer, which is attached, in a peelable manner, to the adhering layer of the dicing tape; and the water contact angle of the surface on the side of the adhering layer which is in close contact with the adhesive layer is 110 DEG or less, and the arithmetic average surface roughness Ra is 1.0 [mu]m or less.

Description

Diced wafer

The present invention relates to a diced chip mucous film. In more detail, the present invention relates to a dicing die film that can be used in the manufacturing process of semiconductor devices.

In the manufacturing process of semiconductor devices, in the process of obtaining a semiconductor wafer with an adhesive film equivalent to the size of the wafer for die bonding, that is, a semiconductor wafer with an adhesive layer for die bonding, there is a method of using a die-cut die bonding film Happening. The dicing die attach film has a size corresponding to the semiconductor wafer to be processed, for example, it has a die dicing tape including a substrate and an adhesive layer, and a die attach film that is peelably attached to the adhesive layer side (adhesive Floor).

As one of the methods for obtaining a semiconductor wafer with an adhesive layer using a dicing die bond film, there is known a method through the following steps, which is used to expand the dicing tape in the die bond film to bond the die The membrane is cut off. In this method, first, a semiconductor wafer is attached to the die attach film of the dicing die attach film. For example, the semiconductor wafer is then cut together with the die attach film and processed into a single piece into a plurality of semiconductor wafers.

Secondly, in order to cut the adhesive film on the dicing tape, an expansion device is used to stretch the dicing tape of the dicing adhesive film in a two-dimensional direction including the radial and circumferential directions of the semiconductor wafer. In this expansion step, the semiconductor wafer on the die-bonding film is also cut at a location equivalent to the cut site in the die-bonding film, and the semiconductor wafer is singulated into plural pieces on the die-cutting die film or dicing tape A semiconductor wafer.

Secondly, in order to expand the separation distance of the plurality of semiconductor wafers with adhesive films after being cut on the dicing tape, an expansion step is performed again. Secondly, after the cleaning step, for example, the pin member of the pick-up mechanism is used to lift each semiconductor wafer and the adhesive film of the equivalent size of the die attached to it from the lower side of the dicing tape, and then pick it up from the dicing tape. In this way, a semiconductor chip with an adhesive crystal film or adhesive layer is obtained. The semiconductor chip of the adhesive layer is fixed on the attached body such as the mounting substrate by die bonding via the adhesive layer.

The related technology of the diced wafer used as described above is described in, for example, the following Patent Documents 1-3. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-2173 [Patent Document 2] Japanese Patent Laid-Open No. 2010-177401 [Patent Document 3] Japanese Patent Laid-Open No. 2016-115804

[The problem to be solved by the invention]

In recent years, in accordance with the demand for high capacitance of semiconductors, the multilayering of circuit layers and the thinning of silicon layers have continued to develop. However, the thickness (total thickness) of the circuit layer increases due to the multilayering of the circuit layer, so the ratio of the resin contained in the circuit layer tends to increase. As a result, the multilayered circuit layer and the thinned silicon layer The difference in the linear expansion coefficient becomes significant, and the semiconductor wafer easily warps. Therefore, when using the previous die-cutting die-bonding film, especially the semiconductor chip with the circuit layer attached to the die-cutting film obtained after dicing, there is an expansion step (the following cold expansion and room temperature expansion) and subsequent (For example, during the cleaning step, before picking up, etc.) peeling (floating) is likely to occur at the interface between the adhesive layer of the dicing tape and the die attach film. If floating occurs, the semiconductor wafer will easily slip off after the expansion step (cleaning step, operation, etc.).

The present invention was completed in view of the above-mentioned problems, and its object is to provide a diced die sticking film that is unlikely to float between the adhesive layer and the adhesive layer during cold expansion and normal temperature expansion, and thereafter. [Technical means to solve the problem]

The inventors of the present invention conducted intensive studies in order to achieve the above-mentioned objects, and found that if the following diced crystal bonding film is used, it will be between the adhesive layer and the adhesive layer during cold expansion and normal temperature expansion, and thereafter. The dicing adhesive film is not prone to floating, and the chip dicing adhesive film is provided with: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer that is releasably adhered to the adhesive in the dicing tape And the water contact angle of the surface of the adhesive layer on the side closely connected with the adhesive layer is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. The present invention was completed based on these findings.

That is, the present invention provides a dicing die attach film comprising: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer that is releasably adhered to the above-mentioned dicing tape Adhesive layer; and the water contact angle of the surface of the adhesive layer close to the side of the adhesive layer is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less.

The chip adhesive film of the present invention includes a chip tape and an adhesive layer. The dicing tape has a laminated structure including a substrate and an adhesive layer. The adhesive layer is peelably attached to the adhesive layer in the dicing tape. The diced die attach film of this structure can be used to obtain a semiconductor wafer with an adhesive layer during the manufacturing process of a semiconductor device.

In the manufacturing process of a semiconductor device, as described above, in order to obtain a semiconductor wafer with an adhesive layer, there are cases where an expansion step using a dicing die attach film, that is, an expansion step for severing, is performed. In this expansion step, the cutting force needs to be properly applied to the adhesive layer on the dicing tape in the dicing adhesive film. Regarding the adhesive layer of the dicing tape in the dicing adhesive film of the present invention, the water contact angle of the surface on the side where the adhesive layer is adhered is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. According to the diced chip adhesive film of the present invention having such a configuration, the adhesive layer and the adhesive layer are moderately excellent in adhesion, and the peeling (floating) between the adhesive layer and the adhesive layer can be suppressed during and after the expansion step. From).

In addition, in the diced chip adhesive film of the present invention, it is preferable that the contact angle of the above-mentioned surface of the adhesive layer (the surface on the side where the adhesive layer is in close contact) with water and diiodomethane is calculated according to the Kaelble Uy formula The value of the polar component of the surface free energy is 0.10 or more. According to the diced chip adhesive film of the present invention having such a constitution, the difference between the polar components of the surface of the adhesive layer and the surface of the adhesive layer becomes small, and the affinity between the surface of the adhesive layer and the surface of the adhesive layer becomes high. Therefore, the adhesive layer and the adhesive layer The adhesion of the layer becomes more moderate, which can further suppress the peeling (floating) between the adhesive layer and the adhesive layer during and after the expansion step.

In addition, in the chip adhesive film of the present invention, the adhesive layer preferably contains an acrylic polymer, and the acrylic polymer includes a hydrocarbon-containing (meth)acrylate that may have an alkoxy group and a hydroxyl group The monomer is used as the monomer component. According to the chip adhesive film of the present invention having such a structure, an adhesive layer having a surface with a water contact angle of 110° or less and an arithmetic mean surface roughness Ra of 1.0 μm or less can be easily designed.

The aforementioned adhesive layer preferably contains a polyisocyanate compound as a crosslinking agent. According to the diced chip adhesive film of the present invention having such a structure, an adhesive layer having a surface with a water contact angle of 110° or less and an arithmetic mean surface roughness Ra of 1.0 μm or less can be easily designed, and it can be easily designed It is possible to distinguish between the state where the adhesive layer expresses relatively high adhesive force and the state where the adhesive layer expresses relatively low adhesive force. [Effects of Invention]

The diced die attach film of the present invention is not prone to float between the adhesive layer and the adhesive layer during and after the expansion step using the die attach film to obtain a semiconductor wafer with an adhesive layer. Especially when a semiconductor chip with multilayered circuit layers is used, it is not easy to float.

[Cut crystal stick film] The dicing die film of the present invention includes: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer that is releasably adhered to the adhesive layer in the dicing tape. Hereinafter, one embodiment of the diced die stick film of the present invention will be described.

Fig. 1 is a schematic cross-sectional view showing an embodiment of the dicing die stick film of the present invention. As shown in FIG. 1, the dicing die bonding film 1 includes a dicing tape 10 and an adhesive layer 20 laminated on the adhesive layer 12 in the dicing tape 10, and can be used to obtain adhesion in the manufacture of semiconductor devices The expansion step in the process of the semiconductor wafer of the agent layer.

The die-cutting die-bonding film 1 has a disk shape with a size corresponding to a semiconductor wafer that is a processing object in the manufacturing process of a semiconductor device. The diameter of the dicing die attach film 1 is, for example, in the range of 345-380 mm (12-inch wafer corresponding type), 245-280 mm (8-inch wafer corresponding type), and 195-230 mm Within (6 inch wafer corresponding type), or within the range of 495～530 mm (18 inch wafer corresponding type).

The chip dicing tape 10 in the chip bonding film 1 has a laminated structure including a substrate 11 and an adhesive layer 12. The water contact angle of the surface 12a of the adhesive layer 12 on the side where the adhesive layer 20 is in close contact with the chip adhesive film 1 is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less.

(Substrate) The substrate in the dicing tape is an element that functions as a support in the dicing tape or the dicing adhesive film. As the substrate, for example, a plastic substrate (especially a plastic film) can be cited. The above-mentioned substrate may be a single layer, or a laminate of substrates of the same or different species.

As the resin constituting the above-mentioned plastic substrate, for example, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra-low density polyethylene, random copolymer polypropylene, embedded Segment copolymer polypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionic polymer, ethylene-(meth)acrylic acid copolymer, ethylene-(methyl) Polyolefin resins such as acrylate (random, alternating) copolymers, ethylene-butene copolymers, and ethylene-hexene copolymers; polyurethane; polyethylene terephthalate (PET), polynaphthalene Polyester such as ethylene dicarboxylate and polybutylene terephthalate (PBT); polycarbonate; polyimide; polyether ether ketone; polyether imide; aromatic polyamide, wholly aromatic Polyamides such as polyamides; polyphenylene sulfide; fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulose resin; polysiloxane resin, etc. In terms of easy to ensure good heat shrinkability in the substrate, the substrate preferably contains ethylene-vinyl acetate from the viewpoint of maintaining the chip separation distance by using the dicing tape or the local thermal shrinkage of the substrate in the following room temperature expansion step The ester copolymer is the main component.

Furthermore, the main component of the substrate refers to the component that accounts for the largest mass ratio among the constituent components. Only one kind of the above-mentioned resin may be used, or two or more kinds may be used. When the adhesive layer is a radiation-curable adhesive layer as described below, the base material preferably has radiation permeability.

When the base material is a plastic film, the above-mentioned plastic film may be non-aligned or aligned in at least one direction (uniaxial direction, biaxial direction, etc.). When aligned in at least one direction, the plastic film can heat shrink in the at least one direction. If it has heat shrinkability, the outer peripheral part of the semiconductor wafer of the dicing tape can be heat-shrinked, so that the gap between the semiconductor wafers of the singulated adhesive layer can be fixed in an expanded state, so it can Easily pick up semiconductor wafers. In order to make the substrate and the dicing tape have isotropic heat shrinkability, the substrate is preferably a biaxial alignment film. Furthermore, the above-mentioned plastic film aligned in at least one direction can be obtained by extending the unextended plastic film in the at least one direction (uniaxial expansion, biaxial expansion, etc.).

The heat shrinkage rate of the substrate and the dicing tape in the heat treatment test performed under the conditions of a heating temperature of 100°C and a heating time of 60 seconds is preferably 1-30%, more preferably 2-25%, and more It is preferably 3-20%, and particularly preferably 5-20%. The above-mentioned heat shrinkage rate is preferably at least one of the MD direction and the TD direction.

In order to improve the adhesion and retention of the adhesive layer, for example, corona discharge treatment, plasma treatment, frosting treatment, ozone exposure treatment, flame exposure treatment, high pressure treatment can be performed on the surface of the adhesive layer side of the substrate. Physical treatment such as electric shock exposure treatment and ionizing radiation treatment; chemical treatment such as chromic acid treatment; surface treatment such as easy bonding treatment with coating agent (primer). In addition, in order to impart antistatic properties, a conductive vapor deposition layer containing metals, alloys, oxides of these, and the like may be provided on the surface of the substrate. The surface treatment for improving the adhesion is preferably performed on the entire surface of the adhesive layer side of the substrate.

From the standpoint of ensuring the strength for the substrate to function as a support in the dicing tape and the chip bonding film, the thickness of the substrate is preferably 40 μm or more, more preferably 50 μm or more, and more It is preferably 55 μm or more, particularly preferably 60 μm or more. In addition, from the viewpoint of achieving moderate flexibility in the dicing tape and the dicing die attach film, the thickness of the substrate is preferably 200 μm or less, more preferably 180 μm or less, and even more preferably 150 μm or less .

(Adhesive layer) Regarding the adhesive layer in the chip adhesive film of the present invention, as described above, the water contact angle of the surface close to the adhesive layer is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. The diced chip adhesive film of the present invention has such a structure, and the adhesion between the adhesive layer and the adhesive layer is moderately excellent, so that the peeling between the adhesive layer and the adhesive layer can be suppressed during and after the expansion step (Floating).

The arithmetic mean surface roughness (Ra) of the surface (surface 12a) of the adhesive layer close to the adhesive layer is 1.0 μm or less, preferably 0.5 μm or less, and more preferably 0.3 μm or less. The above-mentioned Ra is obtained by measuring the surface of the adhesive layer of the dicing die bond film of the present invention where the adhesive layer is not laminated. The arithmetic average surface roughness can be measured based on JIS B0601.

The water contact angle of the surface (surface 12a) of the adhesive layer on the side close to the adhesive layer is 110° or less, preferably 108° or less, more preferably 105° or less. The above-mentioned water contact angle is obtained by measuring the surface of the adhesive layer of the diced die bond film of the present invention where the adhesive layer is not laminated.

Furthermore, the water contact angle is, for example, 80° or more, preferably 84° or more, and more preferably 88° or more. If the above-mentioned water contact is 80° or more, the fusion of the adhesive layer and the adhesive layer can be suppressed, and the problem that the adhesive layer and the adhesive layer are not peeled off when the adhesive layer and the adhesive layer are deliberately peeled is less likely to occur.

The contact angle of the water and diiodomethane on the surface (surface 12a) of the adhesive layer close to the adhesive layer. The value of the polar component of the surface free energy calculated according to the Kaelble Uy formula is preferably 0.10 or more, more Preferably it is 0.20 or more, More preferably, it is 0.40 or more. If the value of the above-mentioned polar component is 0.10 or more, the difference between the polar component and the surface of the adhesive layer becomes smaller, and the affinity between the surface of the adhesive layer and the surface of the adhesive layer becomes higher, so the adhesion between the adhesive layer and the adhesive layer It becomes more moderate and can further suppress the peeling (floating) between the adhesive layer and the adhesive layer during and after the expansion step. The value of the above-mentioned polar component is γs ^p in the following formula (1) used when the surface free energy is obtained, and can be obtained using the following formula (2) and the following formula (3). ^{γs = γs d + γs p (} 1) γw (1 + cosθw) = 2 (γs d γw d) 1/2 +2 (γs p γw p) 1/2 (2) γi (1 + cosθi) = 2 (γs d γi d) 1 ^/2 ＋2(γs ^p γi ^p ) ^1/2 (3) In the above formulas (1)～(3), γs represents the surface free energy of the adhesive layer, and γs ^d represents the dispersed component of the surface free energy of the adhesive layer, γs ^p represents the polar component of the surface free energy of the adhesive layer, γw represents 72.8 mJ/m ² , γw ^d represents 21.8 mJ/m ² , γw ^p represents 51.0 mJ/m ² , γi represents 50.8 mJ/m ² , γi ^d Represents 48.5 mJ/m ² , γi ^p represents 2.3 mJ/m ² , θw represents the water contact angle on the surface of the adhesive layer, and θi represents the contact angle of diiodomethane on the surface of the adhesive layer. ^{γw, γw d, γw p,} γi, γi d γi ^p and the known literature values.

The adhesive layer of the dicing tape is preferably an adhesive layer (acrylic adhesive layer) containing an acrylic polymer as a base polymer. The aforementioned acrylic polymer is a polymer containing a structural unit derived from an acrylic monomer (a monomer component having a (meth)acrylic acid group in the molecule) as a structural unit of the polymer.

It is preferable that the said acrylic polymer contains the structural unit derived from (meth)acrylate at most by mass ratio. In addition, only one type of acrylic polymer may be used, or two or more types may be used. In addition, in this specification, "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid" (either or both of "acrylic acid" and "methacrylic acid"), and others are the same.

As said (meth)acrylate, the (meth)acrylate which may have the hydrocarbon group containing an alkoxy group may be mentioned, for example. As the (meth)acrylate containing a hydrocarbon group, an alkyl (meth)acrylate, a cycloalkyl (meth)acrylate, an aryl (meth)acrylate, etc. may be mentioned.

As the above-mentioned alkyl (meth)acrylate, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl (meth)acrylate can be mentioned. Ester, pentyl ester, isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester (Lauryl ester), tridecyl ester, tetradecyl ester, cetyl ester, octadecyl ester, eicosyl ester, etc.

As said cycloalkyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl etc. are mentioned, for example. As said aryl (meth)acrylate, for example, phenyl (meth)acrylate and benzyl ester may be mentioned.

Examples of the (meth)acrylate having an alkoxy group-containing hydrocarbon group include those obtained by substituting one or more hydrogen atoms in the hydrocarbon group in the above-mentioned hydrocarbon group-containing (meth)acrylate with an alkoxy group. For example, 2-methoxymethyl, 2-methoxyethyl, 2-methoxybutyl etc. of (meth)acrylic acid can be mentioned.

The above-mentioned hydrocarbon group-containing (meth)acrylates which may have an alkoxy group may be used in one kind or two or more kinds.

In one embodiment, the above-mentioned hydrocarbon group-containing (meth)acrylate which may have an alkoxy group is preferably the total number of carbons in the ester portion (in the case of an alkoxy group, it contains the carbon in the alkoxy group). The total number) is preferably 6-10. Particularly preferred is a (meth)acrylate having a hydrocarbon group containing 6 to 10 carbon atoms in total. In these situations, it is easier to balance the suppression of floating between the adhesive layer and the adhesive layer after the expansion step and the good pick-up in the pick-up step.

Furthermore, in another embodiment, the above-mentioned hydrocarbon group-containing (meth)acrylate that may have an alkoxy group is preferably the total number of carbons in the ester portion (in the case of an alkoxy group, it contains an alkoxy group). The total number of carbons in the base) is 2～4. Particularly preferred is a hydrocarbon group-containing (meth)acrylate having a total number of hydrocarbon groups of 2 to 4 carbon atoms. In these cases, since the above-mentioned hydrocarbon group-containing (meth)acrylates that may have alkoxy groups have relatively high polarity, even if the ratio of polar group-containing monomers is small, the surface of the adhesive layer can be easily The water contact angle becomes 110° or less.

In order to appropriately express the basic characteristics of adhesion and other basic properties obtained by the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group in the adhesive layer, among all the monomer components used to form the acrylic polymer The ratio of the hydrocarbon group-containing (meth)acrylate having an alkoxy group is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more.

In addition, in this specification, the above monomer components do not include compounds having a radiation polymerizable group (for example, having the following second functional group and the following second functional group and) at the stage when the adhesive layer is incorporated into the polymer before radiation is irradiated. Radiation polymerizable carbon-carbon double bond compound).

The acrylic polymer may also include a structure derived from other monomer components that can be copolymerized with the hydrocarbon group-containing (meth)acrylate that may have an alkoxy group in order to modify cohesion, heat resistance, etc. unit. Examples of the above-mentioned other monomer components include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and nitrogen atom-containing monomers. Monomers containing polar groups.

Examples of the above-mentioned carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, butene Acid etc.

As said acid anhydride monomer, maleic anhydride, itaconic anhydride, etc. are mentioned, for example. Examples of the hydroxyl-containing monomer include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethyl) Cyclohexyl) methyl ester and the like.

As said glycidyl group-containing monomer, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, etc. are mentioned, for example.

As the above-mentioned sulfonic acid group-containing monomer, for example, styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide Propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid.

As the phosphoric acid group-containing monomer, for example, 2-hydroxyethyl acryloyl phosphate may, for example, be exemplified.

Examples of the above-mentioned nitrogen-containing monomers include: (meth)acryloline group-containing monomers such as (meth)acryloline group-containing monomers, cyano group-containing monomers such as (meth)acrylonitrile, and (meth)propylene Amido group-containing monomers such as amide.

As the above-mentioned other monomer components, among them, a hydroxyl group-containing monomer and a nitrogen atom-containing monomer (especially an N-𠰌line group-containing monomer) are preferred, and 2-hydroxyethyl (meth)acrylate (2 -Hydroxyethyl (meth)acrylate), (meth)acryloyl 𠰌line. That is, the acrylic polymer preferably contains a structural unit derived from 2-hydroxyethyl (meth)acrylate and/or a structural unit derived from (meth)acryloyl 𠰌line.

Only one type of the above-mentioned other monomer components may be used, or two or more types may be used.

In order to appropriately express the basic characteristics of adhesion and other basic characteristics obtained by the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group in the adhesive layer, the above-mentioned among all the monomer components used to form the acrylic polymer The total ratio of the polar group-containing monomers is preferably 60 mol% or less, and more preferably 50 mol% or less. Furthermore, from the viewpoint that the water contact angle on the surface of the adhesive layer can be easily designed to be 110° or less, the total ratio of the polar group-containing monomers is preferably 10 mol% or more, more preferably 15 mol% the above.

In order to properly express the basic properties of adhesion and other properties obtained by the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group in the adhesive layer, it is derived from all the monomer components used to form the acrylic polymer The ratio of the structural units of the hydroxyl-containing monomer is preferably 5 mol% or more, more preferably 10 mol% or more. Moreover, the said ratio is 80 mol% or less, for example, and may be 70 mol% or less, and 60 mol% or less.

In the case of using the above-mentioned nitrogen-containing monomer as the monomer component for forming the acrylic polymer, the water contact angle of the adhesive layer surface can be easily designed to be 110° or less, which is derived from the viewpoint of The ratio of the structural unit of the nitrogen atom-containing monomer in all the monomer components of the acrylic polymer is preferably 3 mol% or more, more preferably 5 mol% or more. Moreover, the said ratio is 50 mol% or less, for example, 30 mol% or less, and 20 mol% or less may be sufficient as it.

In order to form a crosslinked structure in the polymer backbone, the acrylic polymer may contain a structural unit derived from a multifunctional monomer capable of copolymerizing with the monomer component forming the acrylic polymer. As the above-mentioned multifunctional monomer, for example, hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, new Pentylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, epoxy (meth)acrylate, (e.g. polyglycidyl (meth)acrylate), polyester (meth)acrylate, urethane (meth)acrylate, etc. have ( (Meth)acrylic acid group and other reactive functional group monomers, etc.

Only one kind of the above-mentioned polyfunctional monomer may be used, or two or more kinds may be used. In order to appropriately express the basic characteristics of adhesion and other basic characteristics obtained by the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group in the adhesive layer, the above-mentioned among all the monomer components used to form the acrylic polymer The ratio of the polyfunctional monomer is preferably 40 mol% or less, more preferably 30 mol% or less.

The acrylic polymer preferably has: a structural unit derived from a monomer having a first functional group (for example, the above-mentioned polar group-containing monomer), and a second function derived from a monomer capable of reacting with the first functional group. The structure part of the compound of radical and radiation polymerizable functional group. When the acrylic polymer has such a structure, it is easy to design the following radiation-curable adhesive.

Examples of the combination of the above-mentioned first functional group and the above-mentioned second functional group include: carboxyl and epoxy, epoxy and carboxyl, carboxyl and aziridinyl, aziridinyl and carboxyl, hydroxyl and isocyanide Acid groups, isocyanate groups and hydroxyl groups, etc. Among them, from the viewpoint of the ease of tracking the reaction, a combination of a hydroxyl group and an isocyanate group, and a combination of an isocyanate group and a hydroxyl group are preferred. Among them, the technical difficulty of producing a polymer having a higher reactive isocyanate group is relatively high. On the other hand, from the viewpoint of the ease of production and acquisition of an acrylic polymer having a hydroxyl group, it is preferably The first functional group is a hydroxyl group, and the second functional group is a combination of isocyanate groups.

It is particularly preferable that the acrylic polymer has: a structural unit derived from a hydroxyl-containing monomer, and a carbon-carbon double bond (especially (meth)acryloyl group) and an isocyanate group derived from radiation polymerizability The structure of the compound.

Examples of compounds having radiopolymerizable carbon-carbon double bonds and isocyanate groups include: methacrylic acid isocyanate, 2-acryloxyethyl isocyanate, 2-methyl isocyanate Allyl oxyethyl, isopropenyl-α,α-dimethylbenzyl isocyanate, etc. Among them, 2-propenoxyethyl isocyanate and 2-methacryloxyethyl isocyanate are preferred. In addition, examples of acrylic polymers having hydroxyl groups include those derived from the above-mentioned hydroxyl-containing monomers, or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. Such as the structural unit of ether compounds.

The molar ratio of the structural unit derived from the monomer having the first functional group to the compound having the second functional group and the radiation polymerizable functional group [the former/the latter] is preferably 0.95 or more, more preferably 1.00 or more, It is more preferably 1.05 or more, and particularly preferably 1.10 or more. It is inferred that if the above-mentioned molar ratio is 0.95 or more, the bonding between the first functional group (such as a hydroxyl group) and the second functional group (such as an isocyanate group) is sufficiently promoted, but the adhesive layer still remains to some extent The unreacted first functional group in the acrylic polymer further improves the peeling force between the adhesive layer and the substrate, making it less likely to break the adhesive layer during expansion. The molar ratio may be, for example, 10.00 or less, 5.00 or less, 3.00 or less, 2.00 or less, 1.50 or less, and 1.30 or less.

Particularly preferably, the molar ratio of the hydroxyl-containing monomer to 2-methacryloxyethyl isocyanate [hydroxy-containing monomer/2-methacryloxyethyl isocyanate] is within the above range .

The acrylic polymer is obtained by polymerizing one or more monomer components including acrylic monomers. As a polymerization method, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc. are mentioned.

The adhesive layer or the adhesive forming the adhesive layer may also contain a crosslinking agent. For example, when an acrylic polymer is used as the base polymer, the acrylic polymer can be cross-linked to further reduce low molecular weight substances in the adhesive layer. In addition, the number average molecular weight of the acrylic polymer can be increased.

As said crosslinking agent, a polyisocyanate compound, an epoxy compound, a polyol compound (polyphenol type compound etc.), an aziridine compound, and a melamine compound are mentioned. Among them, polyisocyanate compounds are preferred. In this case, the adhesive layer can be easily designed to have a surface with a water contact angle of 110° or less and an arithmetic average surface roughness Ra of 1.0 μm or less, and it can be easily designed to be able to distinguish the use of the adhesive layer with relatively high performance The state of the adhesive force and the radiation-curing adhesive layer that express the state of relatively low adhesive force. In the case of using a crosslinking agent, the amount used is preferably about 5 parts by mass or less, and more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the base polymer.

The mass average molecular weight of the acrylic polymer (after crosslinking when a crosslinking agent is used) is preferably 300,000 or more (for example, 300,000 to 1.4 million), and more preferably 350,000 or more. If the mass average molecular weight is more than 300,000, the low-molecular-weight substances in the adhesive layer tend to be less, and the contamination of the adhesive layer or semiconductor wafers can be further suppressed.

The adhesive layer can be an adhesive layer (adhesive layer with reduced adhesive force) that can deliberately reduce the adhesion force from the outside during the use of the dicing chip adhesive film, or it can be used for chip bonding Adhesive layer (adhesive layer with non-reducing adhesive force) in which the adhesive force is almost or not reduced due to external action during the use of the film, which can be singulated according to the use of diced chip adhesive film The method or conditions for monolithicization are appropriately selected.

When the adhesive layer is an adhesive layer with a reduced adhesive force, in the manufacturing process or use process of the diced chip adhesive film, it can be distinguished that the adhesive layer has a relatively high adhesive force and the performance is relatively high. The state of low adhesion. For example, when the adhesive layer of the dicing tape is attached to the adhesive layer during the manufacturing process of the dicing adhesive film, or when the dicing adhesive film is used for the dicing step, the adhesive layer can be used to perform relatively better The state of high adhesive force suppresses and prevents the adhesive layer, etc., from floating from the adhesive layer by the adherend. On the other hand, the semiconductor chip of the adhesive layer is picked up by the dicing tape used for the self-dicing die film In the picking step, by reducing the adhesive force of the adhesive layer, picking can be easily performed.

As an adhesive that forms such an adhesive layer with a reduced adhesive force, for example, a radiation curable adhesive and a heat-foaming adhesive can be mentioned. As the adhesive for forming the adhesive layer with reduced adhesive force, one type of adhesive can be used, or two or more types of adhesives can be used.

As the above-mentioned radiation-curable adhesive, for example, an adhesive that is cured by irradiation of electron beams, ultraviolet rays, α-rays, β-rays, γ-rays or X-rays can be used, and it can be particularly preferably used for curing by ultraviolet irradiation. The type of adhesive (ultraviolet curing adhesive).

As the radiation curable adhesive, for example, an additive radiation curable adhesive containing a base polymer such as the acrylic polymer, and a radiation polymerizable monomer having a functional group such as a radiation polymerizable carbon-carbon double bond can be mentioned. Body composition or oligomer composition.

Examples of the above-mentioned radiation polymerizable monomer components include urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetraacrylate. (Meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, etc.

As the radiation polymerizable oligomer component, for example, various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based oligomers may be mentioned. The molecular weight is preferred. It is about 100 to 30,000.

The content of the radiation curable monomer component and the oligomer component in the radiation curable adhesive forming the adhesive layer is, for example, 5 to 500 parts by mass, preferably 40 to 150 parts by mass relative to 100 parts by mass of the base polymer. About mass parts.

In addition, as an additive type radiation-curable adhesive, for example, the one disclosed in Japanese Patent Laid-Open No. 60-196956 can be used.

Examples of the above-mentioned radiation-curable adhesive include an intrinsic type containing a base polymer having a functional group such as a radiation polymerizable carbon-carbon double bond in the polymer side chain or the polymer main chain at the end of the polymer main chain. Radiation-curable adhesive. If such an internal radiation-curable adhesive is used, there is a tendency to suppress the undesirable temporal changes in the adhesive properties caused by the movement of the low molecular weight components in the formed adhesive layer.

As the base polymer contained in the internal radiation curable adhesive, an acrylic polymer is preferred. As a method of introducing a radiation polymerizable carbon-carbon double bond into an acrylic polymer, for example, the following method may be exemplified: a method of polymerizing (copolymerizing) the raw material monomer containing the monomer component having the first functional group to obtain acrylic polymer After the compound, the compound having the second functional group and the radiation polymerizable carbon-carbon double bond is subjected to a condensation reaction or an addition reaction to the acrylic polymer while maintaining the radiation polymerizability of the carbon-carbon double bond.

The above-mentioned radiation-curable adhesive preferably contains a photopolymerization initiator. As the photopolymerization initiator, for example, α-ketol-based compounds, acetophenone-based compounds, benzoin ether-based compounds, ketal-based compounds, aromatic sulfonate chloride-based compounds, photoactive oxime-based compounds, Benzophenone compounds, thioxanthone compounds, camphorquinone, halogenated ketones, phosphine oxides, phosphonates, and the like.

As the above-mentioned α-ketol-based compounds, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethyl Acetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc.

As the above-mentioned acetophenone compound, for example, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2 -Methyl-1-[4-(methylthio)-phenyl]-2-N-𠰌olinylpropane-1 and the like.

As the above-mentioned benzoin ether-based compound, for example, benzoin ethyl ether, benzoin isopropyl ether, anisin methyl ether, etc. may be mentioned. As said ketal type compound, a benzil dimethyl ketal etc. are mentioned, for example.

As said aromatic sulfonyl chloride compound, 2-naphthalenesulfonyl chloride etc. are mentioned, for example. As said photoactive oxime type compound, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, a benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, etc. are mentioned, for example.

As the above-mentioned thioxanthone-based compound, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-Dichlorothioxanthone, 2,4-Diethylthioxanthone, 2,4-Diisopropylthioxanthone, etc.

The content of the photopolymerization initiator in the radiation curable adhesive is, for example, 0.05 to 20 parts by mass relative to 100 parts by mass of the base polymer.

The above-mentioned heat-foaming adhesive is an adhesive containing components (foaming agent, heat-expandable microspheres, etc.) that foam or expand by heating.

As said foaming agent, various inorganic foaming agents or organic foaming agents can be mentioned. As said inorganic foaming agent, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, azides etc. are mentioned, for example. As the above-mentioned organic foaming agent, for example, chlorofluoroalkanes such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethamide, barium azodicarboxylate Azo compounds; p-toluenesulfonamide, diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis(phenylsulfonylhydrazine), allyl bis(sulfonylhydrazine) ) And other hydrazine compounds; p-toluenesulfacarbamide, 4,4'-oxybis(toluenesulfacarbazide) and other semicarbazide compounds; 5-𠰌linyl-1,2,3,4- Thiatriazole and other triazole compounds; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso-p-xylylenedimethamide, etc. N-nitroso compounds, etc.

As the above-mentioned heat-expandable microspheres, for example, microspheres having a structure in which a substance that expands by being easily vaporized by heating is enclosed in a shell. As the above-mentioned substance which is easily vaporized and expanded by heating, for example, isobutane, propane, pentane, etc. may be mentioned. By using an agglutination method or an interfacial polymerization method or the like, a substance that is easily vaporized and expanded by heating is enclosed in a shell-forming substance to produce heat-expandable microspheres. As the above-mentioned shell-forming substance, a substance that exhibits thermal melting properties or a substance that can be broken by the thermal expansion of the enclosed substance can be used. As such a substance, for example, vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polyvinylidene chloride Wait.

As the above-mentioned non-adhesive adhesive layer, for example, a pressure-sensitive adhesive layer may be mentioned. Furthermore, the pressure-sensitive adhesive layer includes an adhesive layer of the following form, that is, regarding the adhesive layer with reduced adhesive force, the adhesive layer formed of the above-mentioned radiation curable adhesive is irradiated in advance by radiation Hardened, but has a certain degree of adhesion. As the adhesive for forming the non-reducing adhesive layer, one type of adhesive can be used, or two or more types of adhesives can be used.

In addition, the entire adhesive layer may be a non-adhesive adhesive layer, or part of the adhesive may be a non-adhesive adhesive layer. For example, when the adhesive layer has a single-layer structure, the entire adhesive layer may be a non-adhesive adhesive layer, or a predetermined part of the adhesive layer (for example, the adhesive target area of the ring frame and located The area outside the central area is the adhesive layer of non-adhesive force, and the other parts (for example, the central area of the semiconductor wafer to be adhered area) are the adhesive layer with reduced adhesive force.

When the adhesive layer has a laminated structure, all the adhesive layers in the laminated structure can be non-adhesive adhesive layers, or a part of the adhesive layers in the laminated structure can be non-adhesive adhesive layers.

Regarding the adhesive layer (radiation-curable adhesive layer that has been irradiated with radiation) that is formed by curing the adhesive layer (radiation-curable adhesive layer that is not irradiated with radiation) by radiation beforehand Layer), even if the adhesive force is reduced by radiation irradiation, the adhesiveness is based on the contained polymer components, and the adhesive layer of the dicing tape can be used in the dicing step, etc. .

In the case of using a radiation-curable adhesive layer that has been irradiated with radiation, the entire adhesive layer can be the radiation-curable adhesive layer that has been irradiated in the direction of the spread of the adhesive layer, or a part of the adhesive layer It is the radiation-curable adhesive layer that has been irradiated with radiation, and the other part is the radiation-curable adhesive layer that has not been irradiated with radiation.

In addition, in this specification, the "radiation-curable adhesive layer" refers to an adhesive layer formed of a radiation-curable adhesive, and includes a radiation-curable adhesive layer that is not irradiated with radiation and the adhesive Both the radiation-curable adhesive layer after the agent layer is cured by radiation irradiation.

As the adhesive for forming the pressure-sensitive adhesive layer, known or commonly used pressure-sensitive adhesives can be used, and acrylic adhesives or rubber-based adhesives using acrylic polymers as the base polymer can be preferably used. When the adhesive layer contains an acrylic polymer as a pressure-sensitive adhesive, the acrylic polymer preferably contains a (meth)acrylate-derived structural unit as the largest structural unit in terms of mass ratio. Things. As the acrylic polymer, for example, the acrylic polymer described as the acrylic polymer that can be contained in the adhesive layer can be used.

In addition to the above components, the adhesive layer or the adhesive forming the adhesive layer can also be formulated with crosslinking accelerators, adhesion imparting agents, anti-aging agents, colorants (pigments, dyes, etc.) and other known or customary adhesives. Layer of additives.

As the above-mentioned coloring agent, for example, a compound that is colored by irradiation with radiation can be exemplified. In the case of containing a compound that is colored by radiation, it is possible to color only the portion irradiated with radiation. The above-mentioned compound colored by radiation irradiation is colorless or light-colored before radiation irradiation, but a compound that becomes colored by radiation irradiation, for example, a leuco dye. The amount of the compound colored by radiation irradiation is not particularly limited, and can be appropriately selected.

The thickness of the adhesive layer is not particularly limited, but when the adhesive layer is an adhesive layer formed of a radiation-curable adhesive, the adhesive force to the adhesive layer before and after radiation curing of the adhesive layer is obtained From the viewpoint of balance, it is preferably about 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably 5 to 25 μm.

(Adhesive layer) The adhesive layer has a function as a thermosetting adhesive for die bonding, and if necessary, it also has the function of maintaining the adhesion of semiconductor wafers and other workpieces to frame members such as ring frames. The adhesive layer can be cut by applying tensile stress, and used by cutting it by applying tensile stress.

The adhesive layer and the adhesive constituting the adhesive layer may contain a thermosetting resin and, for example, a thermoplastic resin as an adhesive component, and may also contain a thermoplastic resin having a thermosetting functional group capable of reacting with the curing agent to form a bond. When the adhesive constituting the adhesive layer contains a thermoplastic resin having a thermosetting functional group, the adhesive does not need to contain a thermosetting resin (epoxy resin, etc.). The adhesive layer may have a single-layer structure or a multilayer structure.

As the above-mentioned thermoplastic resin, for example, natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, Polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon or 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET or PBT , Polyamide imide resin, fluororesin, etc. Only one kind of the above-mentioned thermoplastic resin may be used, or two or more kinds may be used. As the above-mentioned thermoplastic resin, an acrylic resin is preferable because it is easy to ensure the bonding reliability by the adhesive layer due to the low ionic impurities and high heat resistance.

The above-mentioned acrylic resin preferably contains a structural unit derived from a hydrocarbon group-containing (meth)acrylate as the most structural unit in terms of mass ratio. As the hydrocarbon group-containing (meth)acrylate, for example, the hydrocarbon group-containing (meth)acrylate exemplified as the hydrocarbon group-containing (meth)acrylate forming the acrylic polymer that can be contained in the adhesive layer can be exemplified Acrylate.

The above-mentioned acrylic resin may also contain structural units derived from other monomer components that can be copolymerized with the hydrocarbon group-containing (meth)acrylate. Examples of the above-mentioned other monomer components include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, acrylamide, propylene Functional group-containing monomers such as nitrile, various polyfunctional monomers, etc., specifically, those exemplified as other monomer components constituting the acrylic polymer that can be contained in the adhesive layer can be used.

When the adhesive layer contains a thermoplastic resin and a thermosetting resin, examples of the thermosetting resin include epoxy resins, phenolic resins, amino resins, unsaturated polyester resins, and polyurethane resins. Ester resin, silicone resin, thermosetting polyimide resin. Only one kind of the above-mentioned thermosetting resin may be used, or two or more kinds may be used. Since there is a tendency that the content of ionic impurities, etc., which may cause corrosion of the semiconductor wafer to be bonded, is small, the thermosetting resin is preferably an epoxy resin. In addition, as the hardener of the epoxy resin, a phenol resin is preferable.

Examples of the above-mentioned 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 , Fu type, phenolic novolac type, o-cresol novolac type, trihydroxyphenylmethane type, tetraphenol ethane type, hydantoin type, triglycidyl isocyanurate type, glycidylamine type The epoxy resin and so on. Among them, from the viewpoint of being rich in reactivity with phenolic resins as hardeners and excellent in heat resistance, preferred are novolac type epoxy resins, biphenyl type epoxy resins, and trihydroxyphenylmethane type ring Oxygen resin, tetraphenol ethane type epoxy resin.

Examples of phenol resins that can function as hardeners for epoxy resins include novolac type phenol resins, resol type phenol resins, polyhydroxystyrenes such as poly(p-hydroxystyrene), and the like. As a novolak type phenol resin, a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tertiary butylphenol novolak resin, a nonylphenol novolak resin, etc. are mentioned, for example. Only one kind of the above-mentioned phenol resin may be used, or two or more kinds may be used. Among them, from the viewpoint that when used as a hardening agent for epoxy resins as adhesives for crystal bonding, there is a tendency to increase the connection reliability of the adhesives, preferably phenol novolak resins and phenol aralkyl resins .

In the adhesive layer, from the viewpoint of allowing the curing reaction of the epoxy resin and the phenol resin to proceed sufficiently, the phenol resin is based on the hydroxyl groups in the phenol resin per equivalent of epoxy groups in the epoxy resin component. It is preferably contained in an amount of 0.5 to 2.0 equivalents, more preferably 0.7 to 1.5 equivalents.

When the adhesive layer contains a thermosetting resin, from the viewpoint of appropriately expressing the function as a thermosetting adhesive in the adhesive layer, the content of the thermosetting resin is relative to the total amount of the adhesive layer The mass is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass.

When the adhesive layer contains a thermoplastic resin having a thermosetting functional group, as the thermoplastic resin, for example, a thermosetting functional group-containing acrylic resin can be used. The acrylic resin in the thermosetting functional group-containing acrylic resin preferably contains a structural unit derived from a hydrocarbon group-containing (meth)acrylate as the most structural unit in terms of mass ratio. As this hydrocarbon group-containing (meth)acrylate, for example, what is exemplified as the hydrocarbon group-containing (meth)acrylate forming the acrylic polymer that can be contained in the adhesive layer.

On the other hand, as a thermosetting functional group in the acrylic resin containing a thermosetting functional group, a glycidyl group, a carboxyl group, a hydroxyl group, an isocyanate group, etc. are mentioned, for example. Among them, glycidyl and carboxyl groups are preferred. That is, as the acrylic resin containing a thermosetting functional group, a glycidyl group-containing acrylic resin and a carboxyl group-containing acrylic resin are particularly preferred. Furthermore, it is preferable to contain a thermosetting functional group-containing acrylic resin and a curing agent. As the curing agent, for example, a crosslinking agent that can be contained in the radiation-curable adhesive for forming the adhesive layer may be mentioned. Illustrator. When the thermosetting functional group in the thermosetting functional group-containing acrylic resin is a glycidyl group, it is preferable to use a polyphenol-based compound as the curing agent. For example, the various phenolic resins described above can be used.

For the adhesive layer before hardening for crystal bonding, in order to achieve a certain degree of crosslinking, for example, it is preferable to preliminarily blend a polyfunctional compound as a crosslinking component in the resin composition for forming the adhesive layer. The sexual compound can react with the functional group at the end of the molecular chain of the resin that may be contained in the adhesive layer to bond. Such a configuration is preferable from the viewpoint of improving the adhesive properties of the adhesive layer at high temperatures, and from the viewpoint of improving the heat resistance.

As said crosslinking component, a polyisocyanate compound can be mentioned, for example. As the polyisocyanate compound, for example, toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyol and diisocyanate can be mentioned. Moreover, as the said crosslinking component, you may use together other polyfunctional compound, such as an epoxy resin, and a polyisocyanate compound.

From the viewpoint of improving the cohesive force of the formed adhesive layer, the content of the crosslinking component in the resin composition for forming the adhesive layer is relative to the resin having the above-mentioned functional group capable of reacting with the crosslinking component to bond 100 parts by mass is preferably 0.05 parts by mass or more, and from the viewpoint of improving the adhesive force of the formed adhesive layer, it is preferably 7 parts by mass or less.

The adhesive layer preferably contains a filler. By blending fillers into the adhesive layer, the electrical conductivity, thermal conductivity, and elastic modulus of the adhesive layer can be adjusted. As the filler, inorganic fillers and organic fillers may be mentioned, and inorganic fillers are particularly preferred.

As inorganic fillers, for example, in addition to aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, In addition to crystalline silicon dioxide and amorphous silicon dioxide, examples of simple metals such as aluminum, gold, silver, copper, and nickel, or alloys, amorphous carbon black, graphite, etc. The filler may have various shapes such as spherical, needle-like, and sheet-like shapes. As the above-mentioned filler, only one kind may be used, or two or more kinds may be used.

The average particle size of the above filler is preferably 0.005 to 10 μm, more preferably 0.005 to 1 μm. If the above-mentioned average particle size is 0.005 μm or more, the wettability and adhesiveness to adherends such as semiconductor wafers are further improved. If the average particle size is 10 μm or less, the effect of the filler added for imparting the above-mentioned characteristics can be made sufficient, and heat resistance can be ensured. In addition, the average particle diameter of the filler can be determined using, for example, a photometric particle size distribution meter (for example, a brand name "LA-910", manufactured by Horiba Manufacturing Co., Ltd.).

The adhesive layer may also contain other ingredients as needed. Examples of the above-mentioned other components include hardening catalysts, flame retardants, silane coupling agents, ion scavengers, dyes, and the like. Only one type of the above-mentioned other additives may be used, or two or more types may be used.

As said flame retardant, antimony trioxide, antimony pentoxide, brominated epoxy resin, etc. are mentioned, for example.

As the silane coupling agent, for example, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propylmethyl diethoxysilane, etc.

Examples of the ion scavenger include: hydrotalcite, bismuth hydroxide, hydrous antimony oxide (for example, "IXE-300" manufactured by Toagosei Co., Ltd.), zirconium phosphate with a specific structure (for example, "IXE-100"), magnesium silicate (such as "KYOWAAD 600" manufactured by Concord Chemical Industry Co., Ltd.), aluminum silicate (such as "KYOWAAD 700" manufactured by Concord Chemical Industry Co., Ltd.), etc.

Compounds capable of forming complexes with metal ions can also be used as ion traps. As such a compound, a triazole type compound, a tetrazole type compound, and a bipyridine type compound are mentioned, for example. Among them, from the viewpoint of the stability of the complex formed with a metal ion, a triazole-based compound is preferred.

As the above-mentioned triazole compound, for example, 1,2,3-benzotriazole, 1-{N,N-bis(2-ethylhexyl)aminomethyl}benzotriazole, carboxybenzene Triazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole , 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl) Benzotriazole, 2-(2-hydroxy-5-third octylphenyl) benzotriazole, 6-(2-benzotriazole)-4-third octyl-6'-third Butyl-4'-methyl-2,2'-methylene bisphenol, 1-(2',3'-hydroxypropyl)benzotriazole, 1-(1,2-dicarboxydiethyl) ) Benzotriazole, 1-(2-ethylhexylaminomethyl)benzotriazole, 2,4-ditertiary pentyl-6-{(H-benzotriazole-1-yl)methan Yl)phenol 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)-5-(1,1-di Methylethyl)-4-hydroxy, 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl] octyl propionate, 3 -[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionic acid 2-ethylhexyl ester, 2-(2H-benzo Triazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzo Triazol-2-yl)-4-tert-butylphenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl) )-Benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di Tripentylphenyl) benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chloro-benzotriazole, 2-(2-hydroxy-3, 5-bis(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)- 4-(1,1,3,3-tetramethylbutyl)phenol, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzo Triazole, 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid methyl ester, etc.

In addition, prescribed hydroxyl-containing compounds such as hydroquinone compounds, hydroxyanthraquinone compounds, and polyphenol compounds can also be used as ion scavengers. Specific examples of such hydroxyl-containing compounds include: 1,2-benzenediol, alizarin, anthracenol, tannin, gallic acid, methyl gallate, pyrogallol, etc. .

The thickness of the adhesive layer (in the case of a laminate, the total thickness) is not particularly limited, and is, for example, 1 to 200 μm. The upper limit is preferably 100 μm, more preferably 80 μm. The lower limit is preferably 3 μm, more preferably 5 μm.

In the chip adhesive film of the present invention, the peeling force between the adhesive layer and the adhesive layer in the T-type peel test under the conditions of a temperature of 23°C and a peeling speed of 300 mm/min is preferably 0.3 N/20 mm or more, more preferably 0.5 N/20 mm or more, and still more preferably 0.7 N/20 mm or more. If the above-mentioned peeling force is 0.3 N/20 mm or more, the adhesion between the adhesive layer and the adhesive layer can be made moderate. When the expansion step is performed without radiation curing, it is easy to suppress the expansion step and Subsequent peeling (floating) between the adhesive layer and the adhesive layer.

In addition, the higher the peel force, the better, but the upper limit may be, for example, 10 N/20 mm, 5.0 N/20 mm, or 3.0 N/20 mm. In addition, with regard to the chip adhesive film using a radiation-curable adhesive for the adhesive layer, it is preferable that the peeling force of the adhesive layer before radiation curing (the peeling force in the T-type peeling test before ultraviolet curing) is the above value.

In the diced chip adhesive film of the present invention, the peeling force between the adhesive layer and the adhesive layer after radiation curing in a T-type peel test at a temperature of 23°C and a peeling speed of 300 mm/min It is preferably 0.3 N/20 mm or less, and more preferably 0.2 N/20 mm or less. If the above-mentioned peeling force is 0.3 N/20 mm or less, it is easy to achieve good pick-up in the pick-up step after radiation curing.

The diced die sticking film can also have an isolation film. Specifically, each diced mucosal film may have a sheet-like form of an isolation film, or the isolation film may have a long strip shape on which a plurality of diced mucous films are arranged and wound the isolation film. Become a reel form.

The isolation film is used to cover and protect the elements of the surface of the adhesive layer of the chip adhesive film, and is peeled from the film when the chip adhesive film is used. As the separation film, for example, a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate-based release agent may be used. Plastic film or paper coated on the surface. The thickness of the isolation film is, for example, 5 to 200 μm.

The dicing die-cutting film 1 as one embodiment of the die-cutting die-cutting film of the present invention is manufactured, for example, as follows.

First, the substrate 11 can be obtained by forming a film by a known or commonly used film forming method. As the above-mentioned film forming method, for example, a calendering film forming method, a casting method in an organic solvent, a pneumatic extrusion method in a closed system, a T die extrusion method, a co-extrusion method, a dry lamination method, etc. can be mentioned.

Then, after coating the composition (adhesive composition) for forming the adhesive layer 12 on the substrate 11 to form a coating film, the coating film may be cured by desolventizing or hardening as necessary to form an adhesive The agent layer 12, the above composition includes an adhesive and a solvent for forming the adhesive layer 12, etc. As a method of the said coating, a well-known or usual coating method, such as roll coating, screen coating, and gravure coating, can be mentioned, for example. In addition, as the solvent removal conditions, for example, the temperature is 80 to 150°C and the time is 0.5 to 5 minutes.

In addition, after the adhesive composition is applied on the separator to form a coating film, the coating film may be cured under the solvent removal conditions described above to form the adhesive layer 12. Then, the adhesive layer 12 is attached to the base material 11 together with the release film. In this way, the dicing tape 10 can be manufactured. Furthermore, when the method of transferring the adhesive layer 12 formed on the release film to the substrate 11 is used, in order to set the Ra of the surface 12a of the adhesive layer 12 to 1.0 μm or less, it is preferable to use Release the release film with smaller Ra on the treated surface (adhesive composition coating surface).

Regarding the adhesive layer 20, first, a composition (adhesive composition) for forming the adhesive layer 20 containing a resin, a filler, a curing catalyst, a solvent, and the like is produced. Then, after applying the adhesive composition on the separator film to form a coating film, the coating film is cured by solvent removal, curing, or the like as necessary to form the adhesive layer 20. The coating method is not particularly limited, and examples thereof include well-known or commonly used coating methods such as roll coating, screen coating, and gravure coating. In addition, as solvent removal conditions, for example, the temperature is 70 to 160°C and the time is 1 to 5 minutes.

Then, the separation film is peeled off from the dicing tape 10 and the adhesive layer 20, respectively, and the adhesive layer 20 and the adhesive layer 12 are bonded together so that they become bonding surfaces. The bonding can be performed by crimping, for example. At this time, the lamination temperature is not particularly limited, and, for example, it is preferably 30 to 50°C, more preferably 35 to 45°C. In addition, the linear pressure is not particularly limited, and, for example, it is preferably 0.1 to 20 kgf/cm, and more preferably 1 to 10 kgf/cm.

As described above, when the adhesive layer 12 is a radiation-curable adhesive layer, when the adhesive layer 12 is irradiated with radiation such as ultraviolet rays after bonding the adhesive layer 20, for example, the adhesive layer 12 is directed from the base material 11 side. The radiation is irradiated, and the irradiation amount is, for example, 50 to 500 mJ, preferably 100 to 300 mJ.

The area (irradiated area R) that is irradiated as a measure to reduce the adhesive force of the adhesive layer 12 in the chip adhesive film 1 is usually within the bonding area of the adhesive layer 20 in the adhesive layer 12 except for its peripheral edge.的区。 The area. In the case where the irradiation area R is partially provided, it can be performed through a mask formed with a pattern corresponding to the area other than the irradiation area R. In addition, a method of irradiating radiation in dots to form the irradiation area R may also be exemplified.

In this way, for example, the dicing die bonding film 1 shown in FIG. 1 can be produced.

[Method of Manufacturing Semiconductor Device] The chip adhesive film of the present invention can be used to manufacture semiconductor devices. Specifically, a semiconductor device can be manufactured by a manufacturing method including the following steps: on the side of the adhesive layer in the dicing die bond film of the present invention, a split body of a semiconductor wafer including a plurality of semiconductor chips is attached, Or a semiconductor wafer that can be singulated into a plurality of semiconductor chips (sometimes referred to as "step A"); under relatively low temperature conditions, the dicing tape in the dicing die film of the present invention is expanded to at least cut The adhesive layer forms the semiconductor wafer of the adhesive layer (sometimes referred to as "step B"); under relatively high temperature conditions, the dicing tape is expanded to enlarge the semiconductor wafers of the adhesive layer. Space (sometimes called "step C"); and pick up the semiconductor wafer of the above-mentioned adhesive layer (sometimes called "step D").

The above-mentioned divided body of a semiconductor wafer including a plurality of semiconductor chips used in step A, or a semiconductor wafer that can be singulated into a plurality of semiconductor chips can be obtained by the following method. First, as shown in FIGS. 2(a) and 2(b), a dividing groove 30a is formed in the semiconductor wafer W (dividing groove forming step). The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the side of the first surface Wa of the semiconductor wafer W, and wiring structures required for the semiconductor elements have been formed on the first surface Wa (not shown) .

Then, after bonding the wafer processing tape T1 with the adhesive surface T1a to the second surface Wb side of the semiconductor wafer W, the semiconductor wafer W is held on the wafer processing tape T1, and the semiconductor wafer On the first surface Wa side of the wafer W, a rotary blade of a dicing device or the like is used to form a dividing groove 30a of a predetermined depth. The dividing groove 30a is used to divide the semiconductor wafer W into gaps of semiconductor wafer units (in FIGS. 2 to 4, the dividing groove 30a is schematically represented by a thick solid line).

Then, as shown in FIG. 2(c), the wafer processing tape T2 having the adhesive surface T2a is attached to the first surface Wa side of the semiconductor wafer W, and the wafer processing tape T1 is attached from the semiconductor wafer W Peel off.

Then, as shown in FIG. 2(d), while the semiconductor wafer W is held on the wafer processing tape T2, it is thinned by the polishing process from the second surface Wb until the semiconductor wafer W reaches a predetermined level Thickness (wafer thinning step). The grinding process can be performed using a grinding process device equipped with a grinding stone. Through this wafer thinning step, a semiconductor wafer 30A that can be singulated into a plurality of semiconductor wafers 31 is formed in this embodiment.

Specifically, the semiconductor wafer 30A has a portion (connection portion) that connects portions of the wafer that are singulated into a plurality of semiconductor wafers 31 on the second surface Wb side. The thickness of the connecting portion in the semiconductor wafer 30A, that is, the distance between the second surface Wb of the semiconductor wafer 30A and the second surface Wb side tip of the dividing groove 30a is, for example, 1-30 μm, preferably 3-20 μm .

(Step A) In step A, on the adhesive layer 20 side of the dicing die attach film 1, a divided body of a semiconductor wafer including a plurality of semiconductor chips, or a semiconductor wafer that can be singulated into a plurality of semiconductor chips is attached.

In an embodiment of the step A, as shown in FIG. 3(a), the semiconductor wafer 30A held by the wafer processing tape T2 is attached to the adhesive layer 20 of the dicing die bonding film 1. Then, as shown in FIG. 3(b), the wafer processing tape T2 is peeled from the semiconductor wafer 30A.

Furthermore, after the semiconductor wafer 30A is bonded to the adhesive layer 20, the adhesive layer 12 may be irradiated with radiation such as ultraviolet rays from the side of the base material 11. The irradiation amount is, for example, 50 to 500 mJ/cm ² , preferably 100 to 300 mJ/cm ² . The area (irradiated area R shown in FIG. 1) that is irradiated as a measure for reducing the adhesive force of the adhesive layer 12 in the chip adhesive film 1 is, for example, the adhesive layer 20 in the adhesive layer 12 The area other than its periphery.

(Step B) In step B, under relatively low temperature conditions, the dicing tape 10 in the dicing die attach film 1 is expanded to cut at least the adhesive layer 20 to obtain a semiconductor wafer of the adhesive layer.

In an embodiment of step B, firstly, after attaching the ring frame 41 on the adhesive layer 12 of the dicing tape 10 in the chip dicing adhesive film 1, as shown in FIG. 4(a), attach The dicing die bonding film 1 of the semiconductor wafer 30A is fixed to the holder 42 of the expansion device.

Then, as shown in FIG. 4(b), the first expansion step (cold expansion step) under relatively low temperature conditions is performed, the semiconductor wafer 30A is singulated into a plurality of semiconductor wafers 31, and the dicing die is bonded to the film The adhesive layer 20 of 1 is cut into small pieces of the adhesive layer 21 to obtain the semiconductor wafer 31 of the adhesive layer.

In the cold expansion step, the hollow cylindrical jacking member 43 of the expansion device is brought up against the dicing tape 10 on the lower side of the dicing die bonding film 1 in the figure, and the semiconductor wafer 30A will be bonded. The dicing tape 10 of the dicing die bonding film 1 is expanded in a two-dimensional direction including the radial and circumferential directions of the semiconductor wafer 30A.

The expansion is performed under the condition that a tensile stress in the range of 15-32 MPa, preferably 20-32 MPa is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, below 0°C, preferably -20 to -5°C, more preferably -15 to -5°C, and more preferably -15°C. The expansion speed in the cold expansion step (the speed at which the lifting member 43 is raised) is preferably 0.1-100 mm/sec. Moreover, the expansion amount in the cold expansion step is preferably 3-16 mm.

In step B, when a semiconductor wafer 30A that can be singulated into a plurality of semiconductor wafers is used, the semiconductor wafer 30A is singulated into a semiconductor wafer 31 by cutting at a thin and easily broken portion. At the same time, in step B, in the adhesive layer 20 in close contact with the adhesive layer 12 of the expanded dicing tape 10, the deformation of each semiconductor wafer 31 in close contact with each area is suppressed. In this state of deformation suppression, the tensile stress generated in the dicing tape 10 acts on the part in the vertical direction of the dividing groove between the semiconductor wafers 31. As a result, the portion of the adhesive layer 20 in the vertical direction of the dividing groove between the semiconductor wafers 31 is cut. After cutting by expansion, as shown in FIG. 4(c), the lifting member 43 is lowered to release the expanded state of the dicing tape 10.

(Step C) In step C, under relatively high temperature conditions, the dicing tape 10 is expanded to expand the gap between the semiconductor wafers of the adhesive layer.

In an embodiment of step C, first, as shown in FIG. 5(a), the second expansion step (normal temperature expansion step) under relatively high temperature conditions is performed to expand the gap between the semiconductor wafers 31 of the adhesive layer Distance (separation distance).

In step C, the hollow cylindrical lifting member 43 of the expansion device is raised again, and the dicing tape 10 of the dicing die sticking film 1 is expanded. The temperature condition in the second expansion step is, for example, 10°C or higher, preferably 15-30°C. The expansion speed (the speed at which the lifting member 43 is raised) in the second expansion step is, for example, 0.1 to 10 mm/sec, preferably 0.3 to 1 mm/sec. In step C, the separation distance of the semiconductor wafer 31 of the adhesive layer is expanded to the extent that the semiconductor wafer 31 of the adhesive layer can be picked up appropriately from the dicing tape 10 in the following pickup step. After expanding the separation distance by expansion, as shown in FIG. 5(b), the lifting member 43 is lowered to release the expanded state of the dicing tape 10.

From the viewpoint of suppressing the narrowing of the separation distance of the semiconductor wafer 31 of the adhesive layer on the dicing tape 10 after the expansion state is released, it is preferable to compare the semiconductor wafer 31 in the dicing tape 10 before releasing the expansion state. 31 The part of the holding area closer to the outside is heated to shrink it.

After step C, there may also be a cleaning step as needed. The cleaning step uses a cleaning solution such as water to clean the semiconductor wafer 31 side of the dicing tape 10 of the semiconductor wafer 31 with the adhesive layer.

(Step D) In step D (pickup step), the semiconductor wafer of the singulated adhesive layer is picked up. In one embodiment of step D, after the above-mentioned cleaning step is passed as necessary, as shown in FIG. 6, the semiconductor wafer 31 of the adhesive layer is picked up from the dicing tape 10. For example, for the semiconductor wafer 31 of the adhesive layer of the pickup target, the pin member 44 of the pickup mechanism is raised on the lower side of the dicing tape 10 and lifted up by the dicing tape 10, and then the suction jig 45 Perform adsorption retention. In the picking step, the lifting speed of the pin member 44 is, for example, 1-100 mm/sec, and the lifting amount of the pin member 44 is, for example, 50-3000 μm.

The manufacturing method of the above-mentioned semiconductor device may also include other steps besides steps A to D. For example, in one embodiment, as shown in FIG. 7(a), the picked up semiconductor wafer 31 of the adhesive layer is temporarily fixed to the adherend 51 via the adhesive layer 21 (temporary fixing step).

As the adherend 51, for example, a lead frame, a TAB (Tape Automated Bonding) film, a wiring board, a separately produced semiconductor wafer, etc. may be mentioned. The shear adhesive force at 25° C. when the adhesive layer 21 is temporarily fixed is preferably 0.2 MPa or more with respect to the adherend 51, and more preferably 0.2-10 MPa. Regarding the configuration of the adhesive layer 21 with the above-mentioned shear adhesion force of 0.2 MPa or more, the bonding between the adhesive layer 21 and the semiconductor wafer 31 or the adherend 51 due to ultrasonic vibration or heating can be suppressed in the following wire bonding step The surface undergoes shear deformation, and wire bonding is performed appropriately. In addition, the shear adhesive force at 175°C when the adhesive layer 21 is temporarily fixed is preferably 0.01 MPa or more with respect to the adherend 51, and more preferably 0.01-5 MPa.

Then, as shown in FIG. 7(b), the electrode pads (not shown) of the semiconductor wafer 31 and the terminal portions (not shown) of the bonded body 51 are electrically connected via bonding wires 52 (wire bonding step) .

The connection between the electrode pad of the semiconductor chip 31 or the terminal portion of the adherend 51 and the bonding wire 52 can be realized by ultrasonic welding accompanied by heating, so that the adhesive layer 21 is not thermally cured. As the bonding wire 52, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The heating temperature of the wire in the wire bonding is, for example, 80-250°C, preferably 80-220°C. In addition, the heating time is several seconds to several minutes.

Then, as shown in FIG. 7(c), the semiconductor wafer 31 is sealed by the sealing resin 53 for protecting the semiconductor wafer 31 and the bonding wire 52 on the adherend 51 (sealing step).

In the sealing step, thermal curing of the adhesive layer 21 is performed. In the sealing step, the sealing resin 53 is formed by, for example, a transfer molding technique using a mold. As a constituent material of the sealing resin 53, for example, epoxy resin can be used. In the sealing step, the heating temperature for forming the sealing resin 53 is, for example, 165 to 185° C., and the heating time is, for example, 60 seconds to several minutes.

In the case where the curing of the sealing resin 53 is not sufficiently performed in the sealing step, a post-curing step for completely curing the sealing resin 53 is performed after the sealing step. Even when the adhesive layer 21 is not completely thermally cured in the sealing step, the adhesive layer 21 can be completely thermally cured together with the sealing resin 53 in the post-curing step. In the post-curing step, the heating temperature is, for example, 165 to 185°C, and the heating time is, for example, 0.5 to 8 hours.

In the above embodiment, as described above, after the semiconductor wafer 31 of the adhesive layer is temporarily fixed to the adherend 51, the wire bonding step is performed without completely thermally curing the adhesive layer 21. In place of this structure, in the above-mentioned method of manufacturing a semiconductor device, after temporarily fixing the semiconductor wafer 31 of the adhesive layer to the adherend 51, the adhesive layer 21 is thermally cured and then the wire bonding step is performed.

In the above-mentioned method for manufacturing a semiconductor device, as another embodiment, the wafer thinning step shown in FIG. 8 may be performed instead of the wafer thinning step described above with reference to FIG. 2(d). After the process described above with reference to FIG. 2(c), in the wafer thinning step shown in FIG. 8, in the state where the semiconductor wafer W is held on the wafer processing tape T2, The polishing process from the second surface Wb is thinned until the wafer reaches a predetermined thickness, and a semiconductor wafer divided body 30B including a plurality of semiconductor wafers 31 and held by the wafer processing tape T2 is formed.

In the above-mentioned wafer thinning step, the method of polishing the wafer until the dividing groove 30a is exposed on the second surface Wb side (first method) can also be used to polish the wafer from the second surface Wb side until the dividing Before the groove 30a, a method of forming a semiconductor wafer division body 30B by generating a crack between the division groove 30a and the second surface Wb by the pressing force of the rotating grindstone against the wafer (the second method). According to the method used, the depth from the first surface Wa of the dividing groove 30a formed as described above with reference to Figs. 2(a) and 2(b) is appropriately determined.

In FIG. 8, a thick solid line schematically shows the dividing groove 30 a through the first method, or the dividing groove 30 a through the second method, and the cracks formed therefrom. In the manufacturing method of the semiconductor device described above, in step A, the semiconductor wafer split body 30B manufactured by the above method may be used instead of the semiconductor wafer 30A as the semiconductor wafer split body, and proceed as described above with reference to FIGS. 3 to 7 the steps described.

9(a) and 9(b) show step B in this embodiment, that is, the first expansion step (cold expansion step) performed after the semiconductor wafer divided body 30B is attached to the dicing die attach film 1.

In step B of this embodiment, the hollow cylindrical jacking member 43 of the expansion device is brought up against the dicing tape 10 on the lower side of the dicing adhesive film 1 in the figure, and will be attached with The dicing tape 10 of the dicing die bonding film 1 of the semiconductor wafer dividing body 30B expands in a two-dimensional direction including the radial and circumferential directions of the semiconductor wafer dividing body 30B.

The expansion is performed under the condition that a tensile stress in the range of 5-28 MPa, preferably 8-25 MPa, is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, below 0°C, preferably -20 to -5°C, more preferably -15 to -5°C, and more preferably -15°C. The expansion speed in the cold expansion step (the speed at which the jacking member 43 is raised) is preferably 1 to 400 mm/sec. Furthermore, the expansion amount in the cold expansion step is preferably 50 to 200 mm.

According to this cold expansion step, the adhesive layer 20 of the dicing die bond film 1 is cut into small pieces of the adhesive layer 21 to obtain the semiconductor wafer 31 of the adhesive layer. Specifically, in the cold expansion step, in the adhesive layer 20 that is in close contact with the adhesive layer 12 of the expanded dicing tape 10, the regions where the semiconductor wafers 31 of the semiconductor wafer split body 30B are in close contact are deformed It is suppressed. On the other hand, the tensile stress generated in the dicing tape 10 acts on the position in the vertical direction of the dividing groove 30a between the semiconductor wafers 31 in the figure without such deformation suppressing effect. As a result, the part in the vertical direction in the figure of the dividing groove 30a between the semiconductor wafers 31 in the adhesive layer 20 is cut.

In the above-mentioned manufacturing method of a semiconductor device, as another embodiment, a semiconductor wafer 30C manufactured in the following manner may be used instead of the semiconductor wafer 30A or the semiconductor wafer divided body 30B used in step A.

In this embodiment, as shown in FIGS. 10(a) and 10(b), first, a modified region 30b is formed in the semiconductor wafer W. The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the side of the first surface Wa of the semiconductor wafer W, and wiring structures required for the semiconductor elements (not shown) have been formed on the first surface Wa.

Then, after bonding the wafer processing tape T3 with the adhesive surface T3a to the first surface Wa side of the semiconductor wafer W, the semiconductor wafer W is held on the wafer processing tape T3, and the The light spot is aligned with the laser light inside the wafer, and the semiconductor wafer W is irradiated along the predetermined dividing line from the side opposite to the wafer processing tape T3, and the semiconductor wafer W is irradiated by the ablation based on multiphoton absorption. The modified region 30b is formed. The modified region 30b is used to separate the semiconductor wafer W into weakened regions of semiconductor wafer units.

Regarding the method of forming the modified region 30b on the planned dividing line by irradiating laser light in the semiconductor wafer, for example, it is described in detail in Japanese Patent Laid-Open No. 2002-192370, but the laser light irradiation conditions in this embodiment are, for example, Adjust appropriately within the following conditions.

<Laser light irradiation conditions> (A) Laser light Laser light source Semiconductor laser excitation Nd: YAG laser wavelength 1064 nm Laser spot cross-sectional area 3.14×10 ^-8 cm ² Oscillation method Q-switch pulse repetition frequency below 100 kHz Pulse width 1 μs or less, output 1 mJ or less laser light quality TEM00 Polarization characteristic linearly polarized light (B) Condensing lens magnification of 100 times or less NA 0.55 The transmittance of the laser light wavelength is 100% or less (C) For mounting semiconductor substrates The moving speed of the table is below 280 mm/sec

Then, as shown in FIG. 10(c), while the semiconductor wafer W is held on the wafer processing tape T3, it is thinned by the polishing process from the second surface Wb until the semiconductor wafer W reaches a predetermined level. Thus, a semiconductor wafer 30C that can be singulated into a plurality of semiconductor wafers 31 is formed (wafer thinning step).

In the above-mentioned method of manufacturing a semiconductor device, in step A, the thus-produced semiconductor wafer 30C may be used instead of the semiconductor wafer 30A as a semiconductor wafer that can be singulated, and proceed as described above with reference to FIGS. 3 to 7 The steps described.

FIGS. 11(a) and 11(b) show the first expansion step (cold expansion step) performed after bonding the semiconductor wafer 30C to the dicing die stick film 1 in step B in this embodiment.

In the cold expansion step, the hollow cylindrical jacking member 43 of the expansion device abuts against the dicing tape 10 on the lower side of the dicing die bonding film 1 in the figure to rise, and the semiconductor wafer will be attached The dicing tape 10 of the dicing die bonding film 1 of 30C expands in a two-dimensional direction including the radial and circumferential directions of the semiconductor wafer 30C.

The expansion is performed under the condition that a tensile stress in the range of 5-28 MPa, preferably 8-25 MPa, is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, below 0°C, preferably -20 to -5°C, more preferably -15 to -5°C, and more preferably -15°C. The expansion speed in the cold expansion step (the speed at which the jacking member 43 is raised) is preferably 1 to 400 mm/sec. Furthermore, the expansion amount in the cold expansion step is preferably 50 to 200 mm.

Through this cold expansion step, the adhesive layer 20 of the dicing die bond film 1 is cut into small pieces of the adhesive layer 21 to obtain the semiconductor wafer 31 of the adhesive layer. Specifically, in the cold expansion step, the semiconductor wafer 30C forms a crack in the fragile modified region 30b and is singulated into the semiconductor wafer 31. At the same time, in the cold expansion step, in the adhesive layer 20 that is in close contact with the adhesive layer 12 of the expanded dicing tape 10, the deformation of the regions where the semiconductor wafers 31 of the semiconductor wafer 30C are in close contact is suppressed On the other hand, the tensile stress generated in the dicing tape 10 acts on the part located in the vertical direction of the crack formation part of the wafer in the state without such deformation suppression effect. As a result, the portion in the vertical direction in the figure of the crack formation portion located between the semiconductor wafers 31 in the adhesive layer 20 is cut.

In addition, in the above-mentioned method for manufacturing a semiconductor device, the diced die bonding film 1 can be used for the purpose of obtaining a semiconductor wafer with an adhesive layer as described above, and can also be used to obtain a three-dimensional stacking of a plurality of semiconductor wafers. The use of the semiconductor chip of the adhesive layer during installation. Between the semiconductor chips 31 in such three-dimensional mounting, spacers may be interposed together with the adhesive layer 21 or not. [Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited in any way by these examples. In addition, the composition of each monomer component constituting the acrylic polymer P ₂ of the adhesive layer in the examples and comparative examples is shown in the table. Among them, in the table, regarding the unit of each value representing the composition of the composition, the relative value of the monomer component is the relative "mole" in the composition, and the relative value of each component other than the monomer component is relative to This acrylic polymer P ₂ is "parts by mass" of 100 parts by mass.

Example 1 (Crystal Cutting Tape) In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 moles of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (HEA) ) 30 mol, acryloline (AM) 30 mol, 0.2 parts by mass relative to 100 parts by mass of the monomer components, benzyl peroxide as a polymerization initiator, and toluene as a polymerization solvent The mixture was stirred at 61°C under a nitrogen atmosphere for 6 hours (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P ₁ is obtained.

Next, a mixture containing the polymer solution containing the acrylic polymer P ₁ , 2-methacryloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was added to Stir for 48 hours at 50°C in an air atmosphere (addition reaction). In the reaction solution, the amount of MOI is 25 mol. Further, in the reaction solution, di-butyltin dilaurate blending amount relative to 100 parts by mass of the acrylic polymer P ₁ is 0.01 parts by mass. By this addition reaction, a polymer solution containing acrylic polymer P ₂ (an acrylic polymer containing structural units derived from an isocyanate compound containing an unsaturated functional group) with a methacrylate group in the side chain is obtained .

Then, 1 part by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) and 2 parts by mass of photopolymerization were added to the polymer solution with respect to 100 parts by mass of acrylic polymer P ₂ The starting agent (trade name "IRGACURE 127", manufactured by BASF Corporation) was mixed, and then toluene was added and diluted to obtain an adhesive composition.

Then, the adhesive composition was applied on the silicone release treatment surface of the PET isolation film (thickness 50 μm) on which the silicone release treatment was applied to form an adhesive composition layer using an applicator. Then, for the composition layer, the solvent was removed by heating at 120° C. for 2 minutes to form an adhesive layer with a thickness of 10 μm on the PET separator.

Then, using a laminator, the EVA film (thickness 125 μm) as the substrate was attached to the exposed surface of the adhesive layer at room temperature. The fitted body was then stored at 50°C for 24 hours. Thus, the dicing tape of Example 1 was produced.

(Adhesive layer) Acrylic polymer A ₁ (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, with a mass average molecular weight of 1.2 million, a glass transition temperature of 0°C, epoxy Value 0.4 eq/kg) 54 parts by mass, solid phenol resin (trade name "MEHC-7851SS", solid at 23°C, manufactured by Minghe Chemical Co., Ltd.) 3 parts by mass, liquid phenol resin (trade name "MEH-8000H", liquid at 23°C, 3 parts by mass of Minghe Chemical Co., Ltd., and silica filler (trade name "SO-C2"; average particle size is 0.5 μm, Admatechs Co., Ltd.) Manufacturing) 40 parts by mass was added to methyl ethyl ketone and mixed, and the concentration was adjusted so that the viscosity at room temperature became 700 mPa·s to obtain an adhesive composition.

Then, the adhesive composition was applied on the silicone release treatment surface of the PET release film (thickness 38 μm) with the silicone release treatment to form a coating film using an applicator. The coating film was desolventized at 130°C for 2 minutes. In this way, an adhesive layer with a thickness of 10 μm in Example 1 was fabricated on the PET separator.

(Production of slicing and sticking film) The PET isolation film was peeled from the dicing tape of Example 1, and the adhesive layer of Example 1 was attached to the exposed adhesive layer. Use hand rollers in lamination. Then, 300 mJ of ultraviolet rays were irradiated from the side of the dicing tape to produce the dicing die attach film of Example 1.

Example 2 The compounding amount of the acrylic polymer P ₂ (acrylic polymer containing structural units derived from an isocyanate compound containing an unsaturated functional group) constituting the adhesive layer was changed to Except for this, the dicing tape and the dicing die attach film of Example 2 were produced in the same manner as in Example 1 except for this.

Example 3 Except that the adhesive layer was not irradiated with ultraviolet rays, the dicing tape and the dicing die attach film of Example 3 were produced in the same manner as in Example 1.

Example 4 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 2 parts by mass, and except that the preparation of Example 4 was performed in the same manner as in Example 3. Slicing tape and dicing adhesive film.

Example 5 Except that the adhesive layer was not irradiated with ultraviolet rays, the dicing tape and the dicing die attach film of Example 5 were produced in the same manner as in Example 2.

Example 6 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 2 parts by mass, and except that the preparation of Example 6 was performed in the same manner as Example 5 Slicing tape and dicing adhesive film.

Example 7 (Crystal Cutting Tape) In a reaction vessel with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, it will contain ethyl acrylate (EA) 50 mol, butyl acrylate (BA) 50 mol, and acrylic acid 2 -A mixture of 20 moles of hydroxyethyl (HEA), 0.2 parts by mass of benzoyl peroxide as a polymerization initiator, and toluene as a polymerization solvent relative to 100 parts by mass of the monomer components at 61°C, Stirring for 6 hours under a nitrogen atmosphere (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P ₁ is obtained.

Next, a mixture containing the polymer solution containing the acrylic polymer P ₁ , 2-methacryloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was added to Stir for 48 hours at 50°C in an air atmosphere (addition reaction). In the reaction solution, the amount of MOI was 18 mol. Further, in the reaction solution, di-butyltin dilaurate blending amount relative to 100 parts by mass of the acrylic polymer P ₁ is 0.01 parts by mass. By this addition reaction, a polymer solution containing acrylic polymer P ₂ (an acrylic polymer containing structural units derived from an isocyanate compound containing an unsaturated functional group) having a methacrylate group in the side chain is obtained .

Then, 1 part by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) and 2 parts by mass of photopolymerization were added to the polymer solution with respect to 100 parts by mass of acrylic polymer P ₂ The starting agent (trade name "IRGACURE 127", manufactured by BASF Corporation) was mixed, and toluene was added to dilute to obtain an adhesive composition.

Then, the adhesive composition was coated on the silicone release treatment surface of the PET isolation film (thickness 50 μm) on which the silicone release treatment was applied to form the adhesive composition layer using an applicator. Then, for the composition layer, the solvent was removed by heating at 120° C. for 2 minutes to form an adhesive layer with a thickness of 10 μm on the PET separator.

Then, using a laminator, the EVA film (thickness 125 μm) as the substrate was attached to the exposed surface of the adhesive layer at room temperature. The fitted body was then stored at 50°C for 24 hours. Thus, the dicing tape of Example 7 was produced.

(Production of slicing and sticking film) The PET isolation film was peeled from the dicing tape of Example 7, and the adhesive layer of Example 1 was attached to the exposed adhesive layer. Use hand rollers in lamination. In this way, the dicing die attach film of Example 7 was produced.

Example 8 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 2 parts by mass, and except that the preparation of Example 8 was carried out in the same manner as in Example 7. Slicing tape and dicing adhesive film.

Comparative Example 1 (Crystal Cutting Tape) In a reaction vessel with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 mol of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (HEA) ) A mixture of 20 moles, 0.2 parts by mass relative to 100 parts by mass of the monomer components, of benzyl peroxide as a polymerization initiator, and toluene as a polymerization solvent, was stirred at 61°C under a nitrogen atmosphere for 6 hours (Polymerization). Thereby, a polymer solution containing acrylic polymer P ₁ is obtained.

Next, a mixture containing the polymer solution containing the acrylic polymer P ₁ , 2-methacryloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was added to Stir for 48 hours at 50°C in an air atmosphere (addition reaction). In the reaction solution, the amount of MOI was 18 mol. Further, in the reaction solution, di-butyltin dilaurate blending amount relative to 100 parts by mass of the acrylic polymer P ₁ is 0.01 parts by mass. By this addition reaction, a polymer solution containing acrylic polymer P ₂ (an acrylic polymer containing structural units derived from an isocyanate compound containing an unsaturated functional group) having a methacrylate group in the side chain is obtained .

Then, 0.5 parts by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) and 2 parts by mass of photopolymerization were added to the polymer solution with respect to 100 parts by mass of acrylic polymer P ₂ The starting agent (trade name "IRGACURE 127", manufactured by BASF Corporation) was mixed, and toluene was added to dilute to obtain an adhesive composition.

Then, the adhesive composition was applied on the silicone release treatment surface of the PET isolation film (thickness 50 μm) on which the silicone release treatment was applied to form an adhesive composition layer using an applicator. Then, for the composition layer, the solvent was removed by heating at 120° C. for 2 minutes to form an adhesive layer with a thickness of 10 μm on the PET separator.

Then, using a laminator, the EVA film (thickness 125 μm) as the substrate was attached to the exposed surface of the adhesive layer at room temperature. The fitted body was then stored at 50°C for 24 hours. Thus, the dicing tape of Comparative Example 1 was produced.

(Production of slicing and sticking film) The PET release film was peeled from the dicing tape of Comparative Example 1, and the adhesive layer of Example 1 was attached to the exposed adhesive layer. Use hand rollers in lamination. Thus, the dicing die-cut film of Comparative Example 1 was produced.

Comparative example 2 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 1 part by mass, except that the preparation of Comparative Example 2 was carried out in the same manner as Comparative Example 1. Slicing tape and dicing adhesive film.

Comparative example 3 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 2 parts by mass, except that the preparation of Comparative Example 3 was carried out in the same manner as Comparative Example 1. Slicing tape and dicing adhesive film.

Comparative Example 4 (Crystal Cutting Tape) In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 mol of lauryl methacrylate (LMA), 2-hydroxyethyl methacrylate (HEMA) ) A mixture of 20 moles, 0.2 parts by mass relative to 100 parts by mass of the monomer components, of benzyl peroxide as a polymerization initiator, and toluene as a polymerization solvent, was stirred at 61°C under a nitrogen atmosphere for 6 hours (Polymerization). Thereby, a polymer solution containing acrylic polymer P ₁ is obtained.

Next, a mixture containing the polymer solution containing the acrylic polymer P ₁ , 2-methacryloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was added to Stir for 48 hours at 50°C in an air atmosphere (addition reaction). In the reaction solution, the amount of MOI was 18 mol. Further, in the reaction solution, di-butyltin dilaurate blending amount relative to 100 parts by mass of the acrylic polymer P ₁ is 0.01 parts by mass. By this addition reaction, a polymer solution containing acrylic polymer P ₂ (an acrylic polymer containing structural units derived from an isocyanate compound containing an unsaturated functional group) having a methacrylate group in the side chain is obtained .

Then, 0.5 parts by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) and 2 parts by mass of photopolymerization were added to the polymer solution with respect to 100 parts by mass of acrylic polymer P ₂ The initiator (trade name "IRGACURE 127", manufactured by BASF) was mixed, and toluene was added to dilute to obtain an adhesive composition.

Then, the adhesive composition was applied on the silicone release treatment surface of the PET isolation film (thickness 50 μm) on which the silicone release treatment was applied to form an adhesive composition layer using an applicator. Then, for the composition layer, the solvent was removed by heating at 120° C. for 2 minutes to form an adhesive layer with a thickness of 10 μm on the PET separator.

Then, using a laminator, the EVA film (thickness 125 μm) as the substrate was attached to the exposed surface of the adhesive layer at room temperature. The fitted body was then stored at 50°C for 24 hours. Thus, the dicing tape of Comparative Example 4 was produced.

(Production of slicing and sticking film) The PET release film was peeled from the dicing tape of Comparative Example 4, and the adhesive layer of Example 1 was attached to the exposed adhesive layer. Use hand rollers in lamination. Thus, the dicing die-cut film of Comparative Example 4 was produced.

Comparative example 5 In the preparation of the adhesive layer, the blending amount of the polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Co., Ltd.) was set to 1 part by mass, except that the preparation of Comparative Example 5 was performed in the same manner as Comparative Example 4 Slicing tape and dicing adhesive film.

Comparative example 6 In the production of the adhesive layer, the PET isolation film (thickness 50 μm, the arithmetic average surface roughness of the release treatment surface is 1.0 μm) with the surface that has been subjected to the silicone release treatment is released from the silicone Except that the adhesive composition was applied using an applicator to form an adhesive composition layer on the treated surface, the dicing tape and the dicing mucous film of Comparative Example 6 were produced in the same manner as in Example 2.

＜Evaluation＞ The following evaluations were performed on the diced die-bonding films obtained in the examples and comparative examples. The results are shown in the table.

(1) Surface roughness Using a confocal laser microscope (trade name "shape measuring laser microscope VK-X100", manufactured by Keyence Co., Ltd.), the cut crystals obtained in the examples and comparative examples were adhered with the eyepiece 10 times and the objective lens 20 times The arithmetic average surface roughness (Ra) of the adhesive layer surface in the area where the adhesive layer is not laminated on the crystal film is measured.

(2) Water contact angle Using a contact angle meter "CA-X type" (manufactured by Kyowa Interface Science Co., Ltd.), drop a drop of reagent on the surface of the adhesive layer, and measure the angle at this time to measure the water contact angle.

(3) The value of the polar component of the surface free energy obtained according to the Kaelble Uy formula is the same as the measurement of the water contact angle described above, and the diiodomethane contact angle on the surface of the adhesive layer is measured. Then, the water contact angle measured in the contact angle evaluation is set to θw, and the diiodomethane contact angle is set to θi, and γs ^{p is} obtained from the following equations (2) and (3) as the surface free energy The value of the polarity component. Furthermore, γw is 72.8 mJ/m ² , γw ^d is 21.8 mJ/m ² , γw ^p is 51.0 mJ/m ² , γi is 50.8 mJ/m ² , γi ^d is 48.5 mJ/m ² , and γi ^p is 2.3 mJ/m ² . γw(1＋cosθw)=2(γs ^d γw ^d ) ^1/2 ＋2(γs ^p γw ^p ) ^1/2 (2) γi(1＋cosθi)=2(γs ^d γi ^d ) ^1/2 ＋2(γs ^p γi ^p ) ^1/2 (3)

(4) For the floating of the semiconductor wafer with adhesive film, the product name "ML300-Integration" (manufactured by Tokyo Precision Co., Ltd.) is used as a laser processing device to align the focus point on the inside of the 12-inch semiconductor wafer , Irradiate laser light along a grid-like (10 mm×10 mm) predetermined dividing line to form a modified area inside the semiconductor wafer. The irradiation of laser light is carried out under the following conditions. (A) Laser light laser source Semiconductor laser excitation Nd: YAG laser wavelength 1064 nm Laser spot cross-sectional area 3.14×10 ^-8 cm ² Oscillation mode Q-switch pulse repetition frequency 100 kHz Pulse width 30 ns Output 20 μJ /Pulse laser quality TEM00 40 Polarization characteristics Linear polarization (B) Condensing lens magnification 50 times NA 0.55 Transmittance to the wavelength of the laser light 60% (C) The moving speed of the stage for the semiconductor substrate is 100 mm/sec

After the modified area is formed inside the semiconductor wafer, a protective tape for back grinding is attached to the surface of the semiconductor wafer, and a back grinding machine (trade name "DGP8760", manufactured by DISCO Co., Ltd.) is used to make the thickness of the semiconductor wafer Grind the back side by 30 μm.

The semiconductor wafer formed with the modified region and the dicing ring are attached to the dicing die film obtained in the embodiment and the comparative example. Then, a separation and expander (trade name "DDS2300", manufactured by DISCO Co., Ltd.) was used to cut the semiconductor wafer and the die-attach film. Specifically, first, cold expansion is performed in a cold expander unit under conditions of a temperature of -15°C, an expansion speed of 100 mm/sec, and an expansion amount of 15 mm to cut the semiconductor wafer. After cold expansion, it was confirmed that there was no problem with the severing and the floating of the semiconductor chip with the film attached.

After the slicing of the semiconductor wafer and the adhesive film, the above-mentioned cold expander unit is used to expand at room temperature under the conditions of room temperature, expansion speed of 0.3 mm/sec, and expansion amount of 8 mm. Then, observe the area of the part where the die-bonding film floats from the dicing tape with a microscope (the ratio of the area of the floating die-bonding semiconductor chip when the entire area of the die-bonding film is set to 100%). The case where the area ratio of the floating part is less than 30% is evaluated as ○, the case of 30-50% is evaluated as △, and the case of more than 50% is evaluated as ×.

[Table 1] (Table 1) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Adhesive layer Acrylic polymer P ₂ 100 100 100 100 100 100 100 100 2EHA 100 100 100 100 100 100 - - EA - - - - - - 50 50 BA - - - - - - 50 50 LMA - - - - - - - - HEA 30 30 30 30 30 30 20 20 HEMA - - - - - - - - AM 30 10 30 30 10 10 - - MOI 25 25 25 25 25 25 18 18 Addition reaction catalyst (dibutyltin dilaurate) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Crosslinking agent (CORONATE L) 1 1 1 2 1 2 1 2 Photopolymerization initiator (IRGACURE 127) 2 2 2 2 2 2 2 2 Ultraviolet radiation Have Have no no no no no no Arithmetic average surface roughness Ra[μm] 0.19 0.21 0.10 0.16 0.07 0.12 0.06 0.07 Water contact angle [°] 93.5 92.8 107.5 108.1 107.6 106.5 86.7 91.8 The value of the polar component of the surface free energy calculated according to the Kaelble Uy formula 1.08 1.63 0.45 0.10 0.53 0.38 2.54 1.17 Floating when cut off ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] (Table 2) Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Adhesive layer Acrylic polymer P ₂ 100 100 100 100 100 100 2EHA 100 100 100 - - 100 EA - - - - - - BA - - - - - - LMA - - - 100 100 - HEA 20 20 20 - - 30 HEMA - - - 20 20 - AM - - - - - 10 MOI 18 18 18 18 18 25 Addition reaction catalyst (dibutyltin dilaurate) 0.01 0.01 0.01 0.01 0.01 0.01 Crosslinking agent (CORONATE L) 0.5 1 2 0.5 1 1 Photopolymerization initiator (IRGACURE 127) 2 2 2 2 2 2 Ultraviolet radiation no no no no no Have Arithmetic average surface roughness Ra[μm] 0.06 0.09 0.07 0.07 0.08 1.51 Water contact angle [°] 115.4 115.7 113.1 111.0 110.7 106.4 The value of the polar component of the surface free energy calculated according to the Kaelble Uy formula 0.01 -0.02 0.00 0.07 -0.04 0.10 Floating when cut off × × × △ △ ×

As a summary of the above, the structure of the present invention and its changes are noted below in advance. [1] A dicing chip adhesive film, comprising: a dicing tape having a laminated structure including a substrate and an adhesive layer; and Adhesive layer, which is peelably attached to the adhesive layer in the dicing tape; and The water contact angle of the surface of the adhesive layer close to the adhesive layer is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. [2] The dicing die film as described in [1], wherein the water contact angle is 108° or less (preferably 105° or less). [3] The diced chip adhesive film as described in [1] or [2], wherein the water contact angle is 80° or more (preferably 84° or more, more preferably 88° or more). [4] The diced wafer described in any one of [1] to [3], wherein the arithmetic average surface roughness Ra is 0.5 μm or less (preferably 0.3 μm or less). [5] The diced chip adhesive film as described in any one of [1] to [4], wherein the contact angle between the water used on the surface of the adhesive layer and methyl iodide is calculated according to the Kaelble Uy formula The value of the polar component of surface free energy is 0.10 or more (preferably 0.20 or more, more preferably 0.40 or more).

[6] The diced die attach film according to any one of [1] to [5], wherein the adhesive layer contains an acrylic polymer as a base polymer. [7] The diced die stick film as described in [6], wherein the acrylic polymer contains a hydrocarbon group-containing (meth)acrylate which may have an alkoxy group as a monomer component. [8] The diced die stick film as described in [7], wherein the total carbon number of the ester portion of the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group is 6-10. [9] The dicing die film as described in [6], wherein the total number of carbons in the ester portion of the hydrocarbon group-containing (meth)acrylate which may have an alkoxy group is 2 to 4. [10] The diced wafer described in any one of [7] to [9], wherein among all the monomer components used to form the acrylic polymer, the above-mentioned hydrocarbon-containing group which may have an alkoxy group The ratio of (meth)acrylate is 20 mol% or more (preferably 30 mol% or more, more preferably 40 mol% or more).

[11] The diced wafer described in any one of [6] to [10], wherein the acrylic polymer contains a hydroxyl group-containing monomer as a monomer component. [12] The diced die stick film as described in [11], wherein the hydroxyl-containing monomer is 2-hydroxyethyl (meth)acrylate. [13] The diced wafer described in [11] or [12], wherein the ratio of the hydroxyl-containing monomer in all monomer components used to form the acrylic polymer is 5 to 80 mol% . [14] The diced wafer described in any one of [6] to [13], wherein the acrylic polymer contains a monomer containing a nitrogen atom (preferably a monomer containing an N-𠰌line group, more preferably It is (meth)acryloyl (meth)acrylic acid as a monomer component. [15] The diced chip adhesive film as described in [14], wherein the ratio of the nitrogen atom-containing monomer in all monomer components used to form the acrylic polymer is 3-50 mol%. [16] The diced wafer described in any one of [6] to [15], wherein the hydroxyl-containing monomer and the nitrogen-containing atom in all monomer components used to form the acrylic polymer The total ratio of the monomers is 10-60 mol%.

[17] The diced wafer described in any one of [6] to [16], wherein the acrylic polymer has a structural unit derived from a monomer having a first functional group, and a The structure part of the compound of the second functional group and the radiation polymerizable functional group that reacts with the above-mentioned first functional group. [18] The diced die stick film according to [17], wherein the combination of the first functional group and the second functional group is a combination of a hydroxyl group and an isocyanate group, or a combination of an isocyanate group and a hydroxyl group. [19] The diced die bond film according to [17], wherein the first functional group is a hydroxyl group, and the second functional group is an isocyanate group. [20] The diced wafer described in any one of [17] to [19], wherein the compound having a second functional group and a radiation polymerizable functional group is a carbon-carbon double bond having radiation polymerizable properties (Especially (meth)acryloyl) and isocyanate compounds. [21] The diced wafer described in any one of [17] to [20], wherein the compound having a second functional group and a radiation polymerizable functional group is 2-(meth)propylene isocyanate Oxyethyl ester. [22] The diced wafer described in any one of [17] to [21], wherein the above-mentioned structural unit derived from a monomer having a first functional group and the above-mentioned second functional group and radiation polymerizable The molar ratio of the functional group compound is 0.95 or higher (preferably 1.00 or higher, more preferably 1.05 or higher, and still more preferably 1.10 or higher). [23] The diced wafer described in any one of [17] to [22], wherein the above-mentioned structural unit derived from a monomer having a first functional group and the above-mentioned second functional group and radiation polymerizable The molar ratio of the compound of the functional group is 10.00 or less (preferably 5.00 or less, more preferably 3.00 or less, still more preferably 2.00 or less, still more preferably 1.50 or less, particularly preferably 1.30 or less).

[24] The diced die attach film according to any one of [1] to [23], wherein the adhesive layer contains a crosslinking agent (especially a polyisocyanate compound). [25] The diced die stick film as described in [24], wherein the amount of the crosslinking agent used is 0.1 to 5 parts by mass relative to 100 parts by mass of the base polymer. [26] The diced chip adhesive film according to any one of [1] to [25], wherein the adhesive layer contains a hardening catalyst (especially dibutyltin dilaurate).

1: slicing wafer 10: diced tape 11: Substrate 12: Adhesive layer 12a: surface 20: Adhesive layer 21: Adhesive layer 30A: Semiconductor wafer 30a: Division slot 30B: Semiconductor wafer split body 30b: Modified area 30C: Semiconductor wafer 31: Semiconductor wafer 41: ring frame 42: Holder 43: jack up member 44: Pin member 45: Adsorption fixture 51: the body 52: Bonding wire 53: Sealing resin R: irradiation area T1: Tape for wafer processing T1a: Adhesive surface T2: Tape for wafer processing T2a: Adhesive surface T3: Tape for wafer processing T3a: Adhesive surface W: semiconductor wafer Wa: side 1 Wb: side 2

Fig. 1 is a schematic cross-sectional view showing an embodiment of the dicing die stick film of the present invention. FIGS. 2(a) to (d) show some steps in the manufacturing method of the semiconductor device using the dicing die film shown in FIG. 1. Figures 3(a) and (b) show steps after the step shown in Figure 2. Figures 4(a) to (c) show steps after the steps shown in Figure 3. Figures 5(a) and (b) show steps after the step shown in Figure 4. FIG. 6 shows the steps after the steps shown in FIG. 5. Figures 7(a) to (c) show steps after the step shown in Figure 6. FIG. 8 shows a part of the steps in a variation of the manufacturing method of the semiconductor device using the dicing die film shown in FIG. 1. 9(a) and (b) show some steps in a variation of the manufacturing method of the semiconductor device using the dicing die film shown in FIG. 1. FIGS. 10(a) to (c) show some of the steps in a variation of the manufacturing method of the semiconductor device using the dicing die film shown in FIG. 1. FIGS. 11(a) and (b) show some of the steps in a variation of the manufacturing method of the semiconductor device using the dicing die film shown in FIG. 1.

1: slicing wafer

10: diced tape

11: Substrate

12: Adhesive layer

12a: surface

20: Adhesive layer

R: irradiation area

Claims (4)

A diced chip adhesive film, which has: Dicing tape, which has a laminated structure including a substrate and an adhesive layer; and Adhesive layer, which is peelably attached to the adhesive layer in the dicing tape; and The water contact angle of the surface of the adhesive layer close to the adhesive layer is 110° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. Such as the diced chip adhesive film of claim 1, wherein the contact angle of the surface of the adhesive layer with water and diiodomethane is calculated according to the Kaelble Uy formula. The value of the polar component of the surface free energy is 0.10 or more. According to claim 1 or 2, the chip adhesive film, wherein the adhesive layer contains an acrylic polymer, and the acrylic polymer contains a hydrocarbon group-containing (meth)acrylate that may have an alkoxy group and a hydroxyl-containing monomer As a monomer component. According to claim 3, the chip adhesive film, wherein the adhesive layer contains a polyisocyanate compound as a crosslinking agent.

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