TW201906133A - Cleaved crystal film - Google Patents

Abstract

The topic of the present invention is to provide a dicing die-bonding film having an adhesive layer which is excellent in storage stability, can be cured in a short time, and can perform appropriate wire-bonding after curing. The dicing die-bonding film of the present invention comprises: a dicing tape having a laminated structure including a substrate and an adhesive layer; and a bonding agent layer detachably adhered to the above-mentioned adhesive layer in the dicing tape. The bonding agent layer contains a thermosetting component, a filler, and a curing accelerator. After heating at 130 DEG C for 30 minutes, the amount of generated heat measured by DSC measurement is 60% or less of the amount of heat released before heating, the storage elastic modulus at 130 DEG C is 20 Mpa or more and 4000 Mpa or less after heating.

Description

Cut crystal

The invention relates to a cut crystal and sticky crystal film. More specifically, the present invention relates to a die-cut die-bond film that can be used in the manufacturing process of a semiconductor device.

In the manufacturing process of a semiconductor device, in the process of obtaining a semiconductor wafer having an adhesive film of a size corresponding to a wafer for die attach, that is, a semiconductor wafer with an adhesive layer for a die attach, there is a case where a cut die attach film is used. The cut crystal adhesive film has a size corresponding to a semiconductor wafer as a processing object, for example, a cut crystal tape including a substrate and an adhesive layer, and an adhesive film (adhesive) which is peelably and closely adhered to the side of the adhesive layer. Floor).

As one of the methods for obtaining a semiconductor wafer with an adhesive layer using a die-bonding film, a method is known in which the die-bonding film is cut through extending a die-cutting band in the die-bonding film. In this method, first, a semiconductor wafer is attached to a die-bond film of a die-cut die-bond film. This semiconductor wafer is processed, for example, in such a manner that it can be cut together with the die-bond film and singulated into a plurality of semiconductor wafers. Secondly, in order to cut the die-bonding film on the dicing tape, the stretching device is used to stretch the dicing tape of the die-cutting film to two-dimensional directions including the semiconductor wafer in the radial direction and the circumferential direction. In this extension step, the semiconductor wafer on the die-bond film is also cut at a portion corresponding to the cut-off portion in the die-bond film, and the semiconductor wafer is monolithically formed on the die-bond die-bond film or the die-cut band. A plurality of semiconductor wafers. Secondly, in order to expand the separation distance for the plurality of semiconductor wafers with a sticky crystal film after the cutting on the dicing tape, the extending step is performed again. Secondly, for example, after the washing step, each semiconductor wafer is lifted from the lower side of the dicing tape by the pin member of the picking mechanism together with the die-bonding film of the corresponding size of the wafer that is in close contact with it and picked up from the dicing tape. In this way, a semiconductor wafer with a sticky crystal film or an adhesive layer is obtained. The semiconductor wafer with the adhesive layer is fixed to an adherend such as a mounting substrate via a sticky crystal through the adhesive layer. Techniques related to the dicing die-bonding film used as described above are described in, for example, Patent Documents 1 to 3 below. [Prior Art Literature] [Patent Literature]

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

[Problems to be solved by the invention]

In recent years, there has been a demand for higher functionality, thinner, and smaller semiconductor devices and packages. As one of the countermeasures, a three-dimensional mounting technology has been developed in which semiconductor elements (semiconductor wafers) are laminated in a plurality of steps in the thickness direction to realize high-density integration of semiconductor elements.

As the above-mentioned three-dimensional mounting technology, for example, a technology is known in which a semiconductor wafer, which is a semiconductor wafer with an attached crystal film, is fixed to a substrate such as a substrate, and the additionally obtained adhesion is gradually laminated on the lowest-level semiconductor wafer in order. Crystal wafer of semiconductor wafers. During lamination, the semiconductor wafer with an adhesive film on the upper side may be positioned in a planar direction with respect to the semiconductor wafer on the lower side, so as to avoid the electrode pads on the wire bonding surface (upper surface) of the lower semiconductor wafer. Staggered on top. A semiconductor device (multi-layer laminated semiconductor device) having a multi-layered semiconductor wafer laminated using a die-bond film on the adherend obtained by this technique becomes stepped, and each stage has a semiconductor wafer with a die-bond film attached. A portion (a so-called overhang portion) of the upper surface of the lower semiconductor wafer that projects in a planar direction.

The semiconductor wafer and the adhered system electrically connect the electrode pads on the upper surface of the semiconductor wafer and the terminal portions of the adherend (bond bonding) via bonding wires. The wiring between the electrode pad on the upper surface of the semiconductor wafer for wire bonding and the bonding wire is performed by heating under the combined use of vibrational energy generated by ultrasonic waves and compression energy generated by applying pressure. Here, when wire bonding is performed to the electrode pads existing on the overhang portion of the semiconductor wafer, there is a problem that there is an overhang portion due to a load caused by vibration generated by an ultrasonic wave or a pressure applied to the overhang portion. The case where the semiconductor wafer is shaken to make it difficult to connect, or the overhang portion is bent.

Such a problem can be alleviated by making the die-bonding film used for the semiconductor wafer to some extent harder. However, in order to make the sticky film have a certain degree of adhesion when laminated with a semiconductor wafer with a sticky film, and a certain degree of hardness during wiring, consider after the stacking of the semiconductor wafer to before wiring, so that A method in which the viscous film is hardened to such an extent that the above problems are unlikely to occur. However, if it takes time to sufficiently harden the viscous crystal film, the productivity decreases. Therefore, it is required that the viscous crystal film can be hardened in a short time.

On the other hand, a viscous crystal film that can be cured in a short period of time tends to be easily cured even during storage, and therefore tends to have poor storage stability (especially storage stability at room temperature). That is, the short-term hardenability and storage stability are trade-offs. Therefore, an adhesive film (adhesive layer) is required which is excellent in storage stability and can be hardened in a short time, and can be appropriately wire-bonded (particularly, wire-bonded to an overhang portion) after curing.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a die-cut die-bond film having an adhesive layer that is excellent in storage stability and can be hardened in a short time and can be appropriately wire-bonded after hardening. [Technical means to solve the problem]

The present inventors conducted diligent research in order to achieve the above-mentioned object, and found that if a thermosetting component, a filler, and a hardening accelerator are used and heated at 130 ° C. for 30 minutes, DSC (differential scanning calorimeter) is used. The measured calorific value is less than 60% of the calorific value before heating, and the storage elastic modulus at 130 ° C after heating is 20 MPa or more and 4000 MPa or less. The crystal film also has excellent storage stability, and the adhesive layer can be hardened in a short time, and appropriate wire bonding can be performed after hardening. The present invention has been completed based on these findings.

That is, the present invention provides a cut crystal sticky film including: a cut crystal tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer which is releasably adhered to the above-mentioned cut crystal tape. The adhesive layer; and the adhesive layer contains a thermosetting component, a filler, and a hardening accelerator. After heating at 130 ° C for 30 minutes, the amount of heat measured by DSC is less than 60% of the amount of heat before heating. The above heating The subsequent storage elastic modulus at 130 ° C is above 20 MPa and below 4000 MPa.

The crystal-cut adhesive film of the present invention includes a crystal-cut band and an adhesive layer. The dicing tape has a laminated structure including a substrate and an adhesive layer. The adhesive layer is peelably adhered to the adhesive layer in the dicing tape. The dicing die-bonding film having such a structure can be used to obtain a semiconductor wafer with an adhesive layer in the manufacturing process of a semiconductor device.

In the crystal-cut adhesive film of the present invention, the adhesive layer described above contains a thermosetting component, a filler, and a curing accelerator, as described above. In addition, the amount of heat generated by DSC after heating at 130 ° C for 30 minutes is 60% or less of the amount of heat generated before heating. This means that by heating at 130 ° C. for 30 minutes, more than 60% of the non-hardened thermosetting component in the adhesive layer before heating is cured. By making the adhesive layer in the die-cutting viscous film of the present invention have the above-mentioned structure, the hardening ratio of the adhesive layer of the above-mentioned adhesive layer obtained by heating under a relatively short heating condition is large, so that it can be applied to Hardened in a short time, can improve storage elastic modulus in a short time. In addition, since the hardening ratio of the adhesive layer obtained by heating under a relatively short heating condition is large, hardening does not easily occur even during storage and before heating, that is, excellent storage stability.

Furthermore, in the crystal-cutting viscous film of the present invention, the adhesive layer is as described above, and the storage elastic modulus at 130 ° C. after the heating is 20 MPa or more and 4000 MPa or less. By setting the storage elastic modulus after heating to 20 MPa or more, the adhesive layer can be hardened in a short time and has a certain degree of hardness after hardening, so that appropriate wire bonding can be performed after hardening. In particular, even when the above-mentioned adhesive layer is used in a multi-layer laminated semiconductor device having an overhang portion, it is possible to suppress a load caused by ultrasonic vibration or a load caused by pressurizing the overhang portion at the time of wire bonding. The overhang of the sway can be properly threaded. In addition, by making the storage elastic modulus after the heating to be 4000 MPa or less, the bonding reliability with the adherend and the bonding reliability between the semiconductor wafers are excellent even after curing.

The thermosetting component in the adhesive layer is preferably a thermosetting resin and / or a thermosetting functional group-containing thermoplastic resin. The adhesive layer has a structure using a thermosetting resin or a thermosetting functional group-containing thermoplastic resin as a thermosetting component, has excellent storage stability, can be cured in a short time, and can be appropriately wire-bonded after curing. (Especially proper wire bonding to overhangs).

The adhesive layer preferably has a viscosity of 300 to 100,000 Pa · s at 90 ° C. Multi-layer laminated semiconductor devices generally have a large number of circuit layers, so semiconductor wafers are prone to warp significantly. This is because semiconductor wafers tend to peel off easily. However, if the viscosity of the adhesive layer at 90 ° C. is 300 Pa · s or more, when the die bonding is performed on a semiconductor wafer that is relatively easy to warp, even if the viscosity is reduced due to the heat from the die bonding stage, and the semiconductor When the wafer is warped, peeling of the semiconductor wafer is not easy to occur. In addition, if the viscosity is 100,000 Pa · s or less, even after curing, the bonding reliability with the adherend or the bonding reliability between the semiconductor wafers is more excellent.

The filler in the adhesive layer is preferably silicon dioxide having an average particle diameter of 70 to 300 nm. The average particle diameter is relatively smaller than the average particle diameter of the filler generally used in the adhesive layer of the cut crystal cement film. If silicon dioxide having an average particle size of 300 nm or less, which is relatively smaller than usual, is used as the filler, the surface area of the filler in the adhesive layer is large, and it is presumed that the use of the filler to capture the reaction accelerator suppresses The effect of the reaction accelerator is more excellent in storage stability. In addition, if silicon dioxide having an average particle diameter of 70 nm or more is used as the filler, the hardenability of the adhesive layer is improved, and the hardening of the adhesive layer obtained by heating under a relatively short time condition The ratio tends to increase. In addition, the wettability and adhesion to an adherend such as a semiconductor wafer are further improved. [Effect of the invention]

The crystal-cut adhesive film of the present invention has an adhesive layer which is excellent in storage stability and can be hardened in a short time, and can be appropriately wire-bonded after hardening. Therefore, when a semiconductor wafer with an adhesive layer obtained by using the die-bonding film of the present invention is applied to a multi-layer laminated semiconductor device having overhangs, it has excellent storage stability and can be cured in a short time. In addition, it is possible to suppress the wobble of the overhang portion caused by the vibration caused by the ultrasonic wave or the load caused by the pressure on the overhang portion at the time of the wire bonding, so that the overhang portion can be properly wire-bonded.

Moreover, from the viewpoint of storage stability, the cut crystal adhesive film is generally stored under refrigeration, but in this case, it must be returned to normal temperature during use. Therefore, in the case of refrigerated storage, it takes time to return to normal temperature, which reduces productivity. On the other hand, the cut-to-stick film of the present invention is also excellent in storage stability at normal temperature, and does not need to be restored to normal temperature during use, and is also excellent in productivity.

[Cut crystal sticky film] The cut crystal sticky film of the present invention includes: a cut crystal belt having a laminated structure including a substrate and an adhesive layer; and an adhesive layer which is peelably adhered to the above-mentioned cut crystal belt. The above-mentioned adhesive layer. Hereinafter, one embodiment of the die-cut die-casting film of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing an embodiment of a cut-to-slice cement film according to 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 an adhesive bond in the manufacture of a semiconductor device. An extension step in the process of a semiconductor wafer of an agent layer. The dicing die-bonding film 1 has a disc shape corresponding to the size of a semiconductor wafer to be processed in a semiconductor device manufacturing process. The diameter of the dicing die-bonding film 1 is, for example, in the range of 345 to 380 mm (for 12-inch wafers), 245 to 280 mm (for 8-inch wafers), and 195 to 230 mm. (For 6-inch wafers) or 495 to 530 mm (for 18-inch wafers). The dicing tape 10 in the dicing die-casting film 1 has a laminated structure including a substrate 11 and an adhesive layer 12.

(Adhesive Layer) The adhesive layer 20 has a function of a thermosetting adhesive for sticky crystals, and further has an adhesion function for holding a workpiece such as a semiconductor wafer and a frame member such as a ring frame as needed. The adhesive layer 20 can be cut by applying tensile stress, and is used after being cut by applying tensile stress.

The adhesive layer 20 and the adhesive forming the adhesive layer 20 contain a thermosetting component, a filler, and a curing accelerator. The thermosetting component is preferably at least one of a thermosetting resin and a thermoplastic resin (thermosetting functional group-containing thermoplastic resin) having a curable functional group capable of reacting with a curing agent to form a bond. . That is, it is preferable that the said thermosetting component is a thermosetting resin and / or a thermosetting functional group containing thermoplastic resin. The adhesive layer 20 has a structure using a thermosetting resin or a thermoplastic resin containing a thermosetting functional group as a thermosetting component, has excellent storage stability, can be cured in a short time, and can be appropriately wire-bonded after curing. (Especially proper wire bonding to overhangs). When the adhesive layer 20 contains a thermosetting resin as the thermosetting component, in addition to the thermosetting resin, for example, a thermoplastic resin as a binder component may be included. When the adhesive layer 20 contains a thermosetting functional group-containing thermoplastic resin, the adhesive layer 20 does not need to include a thermosetting resin (epoxy resin or the like). The adhesive layer 20 may have a single-layer structure or a multilayer structure.

Examples of the thermosetting resin include epoxy resin, phenol resin, amine resin, unsaturated polyester resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. The thermosetting resin may be used alone or in combination of two or more. For the reason that the content of ionic impurities and the like that may cause corrosion of a semiconductor wafer that is a target of sticky crystals tends to be small, the above-mentioned thermosetting resin is preferably an epoxy resin. Moreover, as a hardener of an epoxy resin, a phenol resin is preferable.

Examples of the epoxy resin include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, and fluorene. Type, phenol novolac type, o-cresol novolac type, trihydroxyphenylmethane type, tetraphenol ethane type, hydantoin type, isocyanuric acid triglycidyl ester type, glycidylamine type epoxy resin Wait. Among them, novolac-type epoxy resin, biphenyl-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, and tetraphenol are preferred in terms of rich reactivity with a phenol resin as a hardener and excellent heat resistance. Ethane type epoxy resin.

Examples of the phenol resin that can be used as a curing agent for epoxy resins include novolac-type phenol resins, soluble phenol-type phenol resins, and polyhydroxystyrenes such as polyparahydroxystyrene. Examples of the novolac-type phenol resin include a phenol novolak resin, a phenol aralkyl resin, a cresol novolac resin, a third butyl novolac resin, and a nonylphenol novolac resin. These phenol resins may be used alone or in combination of two or more. Among them, from the viewpoint of tending to improve the connection reliability of the adhesive when used as a hardener for epoxy resins as a bonding agent for viscous crystals, phenol novolak resin and phenol aralkyl resin are preferred. .

In the adhesive layer 20, from the viewpoint that the curing reaction between the epoxy resin and the phenol resin is sufficiently advanced, the phenol resin is based on 1 equivalent of the epoxy group in the epoxy resin component. The hydroxyl group is preferably contained in an amount of 0.5 to 2.0 equivalents, and more preferably 0.7 to 1.5 equivalents.

When the adhesive layer 20 contains a thermosetting resin, the content ratio of the thermosetting resin is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass relative to the total mass of the adhesive layer 20. If the content ratio is 10% by mass or more, the function as a thermosetting adhesive is easily and appropriately expressed in the adhesive layer 20, and the storage elastic modulus can be increased, and appropriate wire bonding can be easily achieved (especially for Appropriate wire bonding of overhangs). If the content ratio is 70% by mass or less, the storage elastic modulus is suppressed from becoming too high, and even when the semiconductor wafer is warped in a multi-layer laminated semiconductor device, peeling of the semiconductor wafer is less likely to occur.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Diene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon or 6,6-nylon polyamine resin, phenoxy resin, acrylic resin, PET (polyethylene terephthalate, polyterephthalic acid Saturated polyester resins such as ethylene glycol) or polybutylene terephthalate (polybutylene terephthalate), polyimide resins, fluororesins, and the like. These thermoplastic resins may be used alone or in combination of two or more. As the above-mentioned thermoplastic resin, an acrylic resin is preferable because it is easy to ensure the bonding reliability obtained by using the adhesive layer 20 because there are few ionic impurities and high heat resistance.

The acrylic resin is a polymer containing a structural unit derived from an acrylic monomer (a monomer component having a (meth) acrylfluorene group in the molecule) as a structural unit of the polymer. It is preferable that the said acrylic polymer is a polymer which contains the structural unit derived from a (meth) acrylate at the most by a mass ratio. The acrylic polymer may be used alone or in combination of two or more. In addition, in this specification, "(meth) acrylic" means "acrylic" and / or "methacrylic" (one or both of "acrylic" and "methacrylic") ), And others are the same.

Examples of the (meth) acrylate include a hydrocarbon group-containing (meth) acrylate. Examples of the hydrocarbon group-containing (meth) acrylate include an alkyl (meth) acrylate, a cycloalkyl (meth) acrylate, and an aryl (meth) acrylate. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, third butyl ester, Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, dodecyl (laurate Esters), tridecyl esters, tetradecyl esters, cetyl esters, octadecyl esters, eicosyl esters, and the like. Examples of the cycloalkyl (meth) acrylate include cyclopentyl ester of (meth) acrylic acid and cyclohexyl ester. Examples of the aryl (meth) acrylate include a phenyl ester and a benzyl ester of (meth) acrylic acid. The hydrocarbon group-containing (meth) acrylate may be used alone or in combination of two or more. In order to appropriately express the basic properties such as the adhesiveness obtained by using a hydrocarbon group-containing (meth) acrylate in the adhesive layer 20, the above-mentioned hydrocarbon group-containing (meth) acrylic acid is used to form the total monomer component of the acrylic resin. The ratio of the ester is preferably 40% by mass or more, and more preferably 60% by mass or more.

The acrylic resin may include structural units derived from other monomer components copolymerizable with the hydrocarbon group-containing (meth) acrylate for the purpose of improving the cohesive force and heat resistance. Examples of the other monomer component include a carboxyl group-containing monomer, an acid anhydride monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid-containing monomer, and acrylic monomer. Functional group-containing monomers such as amines and acrylonitriles. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, and fumaric acid. , Butenoic acid, etc. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6 (meth) acrylate. -Hydroxyhexyl ester, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethyl ring) Hexyl) methyl ester and the like. Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, and (meth) acrylamidopropyl Sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloxynaphthalenesulfonic acid, and the like. Examples of the phosphoric acid-containing monomer include 2-hydroxyethyl acrylamidophosphate and the like. These other monomer components may be used alone or in combination of two or more. In order to appropriately express the basic properties such as the adhesiveness obtained by using a hydrocarbon group-containing (meth) acrylate in the adhesive layer 20, the ratio of the other monomer components in the total monomer components used to form the acrylic resin is preferred. It is 60% by mass or less, and more preferably 40% by mass or less.

When the adhesive layer 20 contains a thermoplastic resin, the content ratio of the thermoplastic resin is preferably 3 to 40% by mass, and more preferably 10 to 30% by mass relative to the total mass of the adhesive layer 20. When the content ratio is 3% by mass or more, the storage elastic modulus is suppressed from becoming too high, and even when the semiconductor wafer is warped in a multi-layer laminated semiconductor device, peeling of the semiconductor wafer is less likely to occur. When the content ratio is 40% by mass or less, the storage elastic modulus can be relatively increased, and appropriate wire bonding (especially appropriate wire bonding to the overhang portion) can be easily achieved.

As the thermosetting functional group-containing thermoplastic resin, for example, an acrylic resin containing a thermosetting functional group can be used. It is preferable that the acrylic resin in this thermosetting functional group containing acrylic resin contains the structural unit derived from a (meth) acrylic acid ester as a structural unit which is the largest by mass ratio. Examples of the (meth) acrylic acid ester include the (meth) acrylic acid ester exemplified as the (meth) acrylic acid ester as the acrylic resin forming the thermoplastic resin. On the other hand, examples of the thermosetting functional group in the acrylic resin containing a thermosetting functional group include a glycidyl group, a carboxyl group, a hydroxyl group, and an isocyanate group. Among these, glycidyl and carboxyl groups are preferred. That is, the acrylic resin containing a thermosetting functional group is particularly preferably a glycidyl group-containing acrylic resin and a carboxyl group-containing acrylic resin. In addition, it is preferable to include a curing agent together with the acrylic resin containing a thermosetting functional group. In the case where the thermosetting functional group in the thermosetting functional group-containing acrylic resin is a glycidyl group, a polyphenol compound is preferably used as the curing agent. For example, the above-mentioned various phenol resins can be used.

Regarding the adhesive layer 20 before hardening for the purpose of crystal sticking, in order to achieve a certain degree of cross-linking, for example, it is preferred to react with a functional group at the molecular chain end of the resin which may be contained in the adhesive layer 20. The bonded polyfunctional compound is prepared in advance as a crosslinking component in a composition (adhesive composition) for forming an adhesive layer. Such a structure is preferable from the viewpoint of improving the adhesive property at high temperature of the adhesive layer 20 and the viewpoint of improving the heat resistance. Examples of the crosslinking component include polyisocyanate compounds. Examples of the polyisocyanate compound include methylenephenyl diisocyanate, diphenylmethane diisocyanate, terephthalic acid diisocyanate, 1,5-naphthalene diisocyanate, an adduct of a polyol and a diisocyanate, and the like. The content of the cross-linking component in the adhesive composition is from the viewpoint of increasing the cohesive force of the formed adhesive layer 20 with respect to 100 parts by mass of the resin having the above-mentioned functional group that can be bonded by reacting with the cross-linking component. It is preferably 0.05 parts by mass or more, and from the viewpoint of improving the adhesion of the formed adhesive layer 20, it is preferably 7 parts by mass or less. Moreover, as said crosslinking component, you may use together other polyfunctional compounds, such as an epoxy resin, and a polyisocyanate compound.

The glass transition temperature of the acrylic resin and the thermosetting functional group-containing acrylic resin that can be adjusted in the adhesive layer 20 is preferably -40 to 10 ° C. As the glass transition temperature of the polymer, a glass transition temperature (theoretical value) obtained based on the following Fox equation can be used. The relationship between the glass transition temperature Tg of the Fox-type polymer and the glass transition temperature Tgi of the homopolymer of each constituent monomer in the polymer. In the formula of Fox below, Tg represents the glass transition temperature (° C) of the polymer, Wi represents the mass fraction of the monomer i constituting the polymer, and Tgi represents the glass transition temperature of the homopolymer of the monomer i (° C) ). For the glass transition temperature of homopolymers, literature values can be used, for example, in "New Polymer Library 7 Introduction to Synthetic Resins for Coatings" (Mitsuka Kitaoka, Polymer Society, 1995) or "Acrylics Directory (1997 Edition) ") (Mitsubishi Rayon Co., Ltd.) lists the glass transition temperatures of various homopolymers. On the other hand, the glass transition temperature of the homopolymer of the monomer can also be obtained by a method specifically described in Japanese Patent Laid-Open No. 2007-51271. Fox formula 1 / (273 ＋ Tg) = Σ [Wi / (273 ＋ Tgi)]

The adhesive layer 20 contains a filler as described above. By blending the filler in the adhesive layer 20, physical properties such as electrical conductivity, thermal conductivity, and elastic modulus of the adhesive layer 20 can be adjusted. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are particularly preferred. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and boron nitride. , Silicon dioxide (crystalline silicon dioxide, amorphous silicon dioxide, etc.), in addition to aluminum, gold, silver, copper, nickel and other metal simple substances, or alloys, amorphous carbon black, graphite and the like. The filler may have various shapes such as a spherical shape, a needle shape, and a scale shape. These fillers may be used alone or in combination of two or more. As the filler, in particular, it is easier to adjust the average particle size compared to other fillers, and it is easy to improve storage stability. Further, from the viewpoint of low cost and insulation, silicon dioxide is preferred.

The filler is preferably a carbon-carbon double bond (particularly, a radical polymerizable functional group) having no radiation hardening property on the surface. In the case where the filler has a carbon-carbon double bond which is radiation-hardenable on the surface, it may react with the polymer in the adhesive layer 12 by radiation irradiation. Therefore, by using the above-mentioned carbon-carbon double bond filler having no radiation hardening property on the surface, storage stability is further improved. In the case where a later-described pickup step is performed after the radiation of the adhesive layer 12 is hardened, the semiconductor wafer 31 with the adhesive layer can be more easily picked up from the adhesive layer 12 in this pickup step. As the filler having a carbon-carbon double bond having no radiation hardening property on the surface, a filler that has not been subjected to a surface treatment can be used.

The average particle diameter of the filler is preferably 70 to 300 nm, and more preferably 75 to 250 nm. The average particle diameter is relatively smaller than the average particle diameter of the filler generally used in the adhesive layer of the cut crystal cement film. If a filler having an average particle diameter of 300 nm or less, which is relatively small, is used as the filler, the surface area of the filler in the adhesive layer is large, and it is presumed that the reaction promotion during storage is suppressed by capturing the reaction promoter with the filler The effect of the agent is more excellent in storage stability. In addition, it is estimated that if a filler having an average particle diameter of 70 nm or more is used as the filler, the capture of the hardening accelerator by the filler becomes moderate, and the adhesive layer is improved by maintaining the action of the hardening accelerator. The hardenability of 20 is that the hardening ratio of the adhesive layer 20 obtained by heating under relatively short heating conditions is likely to become larger. Moreover, the wettability and adhesion to an adherend such as a semiconductor wafer are further improved. The average particle diameter of the filler is determined in the following manner. The hardened adhesive layer 20 is embedded in the resin, the cross-section of the adhesive layer is exposed from the embedded resin, and the cross-section is subjected to ion polishing by a CP (cross section polisher) processing device, and then implemented. Conductive treatment and FE-SEM (Field Emission-Scanning Electron Microscope) observation to obtain a reflected electron image. Divide the area of the filler in the captured image by the number of fillers in the image. The average area of the filler was determined and used as the average particle diameter of the filler. The filler is particularly preferably silicon dioxide having an average particle diameter within the above range.

The content ratio of the filler in the adhesive layer 20 is preferably 3 to 60% by mass, and more preferably 20 to 50% by mass relative to the total mass of the adhesive layer 20. If the content ratio is 3% by mass or more, the adhesive layer 20 can be more easily cut in a cold stretching step described later, and a semiconductor wafer with an adhesive layer can be picked up more favorably in a pickup step described later. When the content ratio is 60% by mass or less, the adhesiveness with the adhesive layer 12 and the adhesion between the semiconductor wafers or the adherend and the semiconductor wafers will be better.

As mentioned above, the adhesive layer 20 contains a hardening accelerator. By blending a hardening accelerator into the adhesive layer 20, the hardening reaction of the thermosetting component can be sufficiently advanced or the hardening reaction rate can be increased during the hardening of the adhesive layer 20. Examples of the hardening accelerator include an imidazole-based compound, a triphenylphosphine-based compound, an amine-based compound, and a boron trihalide-based compound. Examples of the imidazole-based compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, trimellitic acid 1-cyanoethyl-2-phenylimidazolium, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ')]-ethyl-s-tri, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-tri , 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-tri, 2,4-diamino-6- [ 2'-methylimidazolyl- (1 ')]-ethyl-s-triisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Methyl-5-hydroxymethylimidazole and the like. Examples of triphenylphosphine-based compounds include triphenylphosphine, tris (p-methylphenyl) phosphine, tris (nonylphenyl) phosphine, diphenyltolylphosphine, tetraphenylphosphonium bromide, and formazan Triphenylphosphonium chloride, methyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium, benzyltriphenylphosphonium chloride, and the like. The triphenylphosphine-based compound also includes a compound having a triphenylphosphine structure and a triphenylboron structure. Examples of such a compound include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenyltriborate, benzyltriphenylphosphonium tetraphenylborate, triphenylphosphinetriphenylborane, and the like. Examples of the amine-based compound include monoethanolamine trifluoroborate, dicyandiamide, and the like. Examples of the boron trihalide compound include boron trichloride. The hardening accelerator may be used alone or in combination of two or more.

The content of the hardening accelerator in the adhesive layer 20 is preferably 0.15 to 10 parts by mass, and more preferably 0.2 to 3 parts by mass based on 100 parts by mass of the thermosetting component. If the content is 0.15 parts by mass or more, the effect of the hardening accelerator is more fully exerted, and hardening of the adhesive layer 20 by heating under heating conditions for a relatively short time is likely to proceed more significantly. When the content is 10 parts by mass or less, storage stability is more excellent.

The adhesive layer 20 may also include other components as needed. Examples of the other components include a flame retardant, a silane coupling agent, an ion trapping agent, and a dye. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyl. Didiethoxysilane and the like. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide, and hydrous antimony oxide (for example, "IXE-300" manufactured by Toa Synthesis Co., Ltd.), and zirconium phosphate of a specific structure (for example, manufactured by Toa Synthesis Co., Ltd. "IXE-100"), magnesium silicate (such as "KYOWAAD 600" manufactured by Kyowa Chemical Industry Co., Ltd.), aluminum silicate (such as "KYOWAAD 700" manufactured by Kyowa Chemical Industry Co., Ltd.), and the like. Compounds capable of forming complexes with metal ions can also be used as ion trapping agents. Examples of such a compound include a triazole-based compound, a tetrazole-based compound, and a bipyridine-based compound. Among these, a triazole-based compound is preferred from the viewpoint of the stability of the complex formed with the metal ion. Examples of such triazole compounds include 1,2,3-benzotriazole, 1- {N, N-bis (2-ethylhexyl) aminomethyl} benzotriazole, and carboxybenzo Triazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-third-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzene Benzotriazole, 2- (2-hydroxy-5-third octylphenyl) benzotriazole, 6- (2-benzotriazolyl) -4-third octyl-6'-third butyl -4'-methyl-2,2'-methylenebisphenol, 1- (2 ', 3'-hydroxypropyl) benzotriazole, 1- (1,2-dicarboxydiethyl) Benzotriazole, 1- (2-ethylhexylaminomethyl) benzotriazole, 2,4-ditripentyl-6-{(H-benzotriazol-1-yl) methyl } Phenol, 2- (2-hydroxy-5-third butylphenyl) -2H-benzotriazole, 3- [3-third butyl-4-hydroxy-5- (5-chloro-2H- Benzotriazol-2-yl) phenyl] 2-ethylhexyl propionate, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl ) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2-hydroxy -5-methylphenyl) benzotriazole , 2- (2-hydroxy-5-third octylphenyl) -benzotriazole, 2- (3-third butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzo Triazole, 2- (2-hydroxy-3,5-di-third-pentylphenyl) 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-benzotriazole, 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] Methyl propionate and so on. In addition, hydroquinone compounds, or specific hydroxyl-containing compounds such as hydroxyanthraquinone compounds and polyphenol compounds can also be used as ion trapping agents. Specific examples of such a hydroxyl-containing compound include 1,2-benzenediol, alizarin, anthraquinol, tannin, gallic acid, methyl gallate, and pyrogallol. These other additives may be used alone or in combination of two or more.

The thickness of the adhesive layer 20 (the total thickness in the case of a laminated body) is not particularly limited, and is, for example, 1 to 200 μm. The upper limit is preferably 100 μm, and more preferably 80 μm. The lower limit is preferably 3 μm, and more preferably 5 μm.

As described above, the adhesive layer 20 has an exotherm measured by DSC after heating at 130 ° C for 30 minutes, which is 60% or less of the exotherm before heating. That is, [the exothermic amount (J / g) measured by DSC after heating at 130 ° C for 30 minutes / the exothermic amount before heating (J / g) × 100] (%) is 60% or less. This means that by heating at 130 ° C for 30 minutes, more than 60% of the non-hardened thermosetting component in the adhesive layer before heating is cured. By making the adhesive layer in the die-cutting viscous film of the present invention have the above-mentioned structure, the hardening ratio of the adhesive layer of the above-mentioned adhesive layer obtained by heating under a relatively short heating condition is large, so that it can be applied to Harden in a short time, can improve storage elastic modulus in a short time. In addition, since the hardening ratio of the adhesive layer obtained by heating under a relatively short heating condition is large, hardening does not easily occur even during storage and before heating, that is, excellent storage stability. The calorific value measured by DSC after heating at 130 ° C for 30 minutes is preferably 50% or less of the calorific value before heating, and more preferably 40% or less. The lower limit can be 0% or 10%.

The exothermic heat measured by DSC before heating of the next agent layer 20 is preferably 20 to 500 J / g, and more preferably 50 to 300 J / g. If the exothermic amount is 20 J / g or more, the adhesive layer 20 can be hardened more by heating under a heating condition for a relatively short time. If the exothermic heat is 500 J / g or less, the adhesive force on the surface of the adhesive layer 20 can be ensured to a certain extent, and the adhesiveness to the semiconductor wafer and the semiconductor wafer is excellent during the use of the die-cut adhesive film.

The exothermic heat measured by DSC after heating the adhesive layer 20 at 130 ° C for 30 minutes is preferably 5 to 60 J / g, and more preferably 10 to 50 J / g. If the exothermic heat is 5 J / g or more, the sealing resin can be cured once in the sealing step after the wire bonding step. If the exothermic amount is 60 J / g or less, the adhesive layer 20 can be hardened more by heating under a relatively short heating condition.

The calorific value measured by DSC above is the total calorific value [J / g] when the adhesive layer 20 is heated from 0 ° C to 350 ° C at a heating rate of 10 ° C / min using a differential scanning calorimeter. The mass of the adhesive layer 20 used for DSC measurement is, for example, 10 to 15 mg.

The exothermic heat before heating measured by DSC and the exothermic heat after heating at 130 ° C for 30 minutes can be determined by the ratio of the thermosetting component in the adhesive layer 20, the amount of the hardening accelerator, the ratio of the filler, and the particles. And so on. Specifically, as the ratio of the thermosetting component increases, the amount of heat generation before heating tends to increase. The greater the amount of hardening accelerator, the greater the progress of hardening in a relatively short period of time, so the tendency of the exothermic heat after heating at 130 ° C for 30 minutes is smaller. It is speculated that the smaller the ratio of the filler and the larger the particle size of the filler, the less the amount of the hardening accelerator captured, the hardening progress in a relatively short period of time becomes larger, and the heat release after heating at 130 ° C for 30 minutes becomes smaller. tendency.

The adhesive layer 20 is as described above, and the storage elastic modulus at 130 ° C. after the heating is 20 MPa or more and 4000 MPa or less. By setting the storage elastic modulus after heating to 20 MPa or more, the adhesive layer can be hardened in a short time and has a certain degree of hardness after hardening, so that appropriate wire bonding can be performed after hardening. In particular, even when the above-mentioned adhesive layer is used in a multi-layer laminated semiconductor device having overhang portions, it is possible to suppress a load due to vibration caused by ultrasonic waves or pressurization of overhang portions during wire bonding. The sway of the overhang can be properly wire-bonded to the overhang. In addition, by making the storage elastic modulus after the heating to be 4000 MPa or less, the bonding reliability with the adherend and the bonding reliability between the semiconductor wafers are excellent even after curing. The upper limit of the storage elastic modulus may be 2000 MPa, 1,000 MPa, or 500 MPa.

The above-mentioned storage elastic modulus is a dynamic storage elastic modulus measured at 130 ° C in a tensile mode under a condition of a frequency of 1 Hz, an initial chuck distance of 10 mm, and a strain of 0.1% using a viscoelasticity measuring device.

The storage elastic modulus can be controlled by the ratio of the thermosetting component in the adhesive layer 20, the ratio of the thermoplastic resin, the amount of the hardening accelerator, the ratio of the filler, and the like. Specifically, the larger the ratio of the thermosetting component, the amount of the hardening accelerator, and the filler, the harder the adhesive layer 20 after heating, and therefore the higher the storage elastic modulus tends to be. On the other hand, the larger the ratio of the thermoplastic resin, the softer the adhesive layer 20 after heating, and therefore the lower the storage elastic modulus tends to be.

The viscosity at 90 ° C. of the adhesive layer 20 is preferably 300 to 100,000 Pa · s. The multi-layer laminated semiconductor device described above generally has a large number of circuit layers, so that the semiconductor wafer is liable to be greatly warped. This is because the semiconductor wafer tends to be easily peeled. However, if the viscosity of the adhesive layer 20 at 90 ° C. is 300 Pa · s or more, when the die bonding is performed on a semiconductor wafer that is relatively easy to warp, even if the viscosity is reduced due to heat from the die bonding stage, and the semiconductor When the wafer is warped, peeling of the semiconductor wafer is not easy to occur. In addition, if the viscosity is 100,000 Pa · s or less, even after curing, the bonding reliability with the adherend or the bonding reliability between the semiconductor wafers is more excellent. The viscosity is preferably from 500 to 50,000 Pa · s, and more preferably from 1,000 to 40,000 Pa · s. The viscosity at 90 ° C of the adhesive layer 20 after being stored at 23 ° C for 28 days is preferably within the above range. The above viscosity is a value measured by a rotary viscometer under the conditions of a gap of 100 μm, a turntable diameter of 8 mm, a heating rate of 10 ° C./min, a strain of 10%, and a frequency of 5 rad / sec.

Next, the increase rate of viscosity (viscosity increase rate) at 90 ° C after storage at 23 ° C for 28 days at the agent layer 20 [{viscosity at 90 ° C after storage at 23 ° C for 28 days (Pa · s)-at 90 ° C The viscosity (Pa · s)} / viscosity at 90 ° C (Pa · s) × 100] (%) is preferably less than 150%, and more preferably less than 100%. If the increase rate of the viscosity is less than 150%, the storage stability is more excellent. The lower limit of the above viscosity increase rate may also be 0%.

(Base material) The base material 11 in the cut crystal band 10 is an element that functions as a support in the cut crystal band 10 or the cut crystal sticky film 1. Examples of the substrate 11 include a plastic substrate (particularly, a plastic film). The substrate 11 may be a single layer, or may be a laminate of the same or different substrates.

Examples of the resin constituting the plastic substrate include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, and block copolymer. Polypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionic polymer, ethylene- (meth) acrylic copolymer, ethylene- (meth) acrylate (Random, alternating) polyolefin resins such as copolymers, ethylene-butene copolymers, ethylene-hexene copolymers; polyurethanes; polyethylene terephthalate (PET), polynaphthalene dicarboxylic acid Polyesters such as ethylene glycol and polybutylene terephthalate (PBT); polycarbonate; polyimide; polyetheretherketone; polyetherimide; aromatic polyimide, fully aromatic polyfluorene Polyamines such as amines; polyphenylene sulfide; fluororesins; polyvinyl chloride; polyvinylidene chloride; cellulose resins; polysiloxane resins. From the viewpoint of maintaining good heat shrinkability in the substrate 11 and easily using the local thermal shrinkage of the dicing tape 10 or the substrate 11 to maintain the wafer separation distance in the normal temperature extension step described later, the substrate 11 preferably contains An ethylene-vinyl acetate copolymer was used as a main component. It should be noted that the main component of the substrate 11 refers to a component having the largest mass ratio among the constituent components. These resins may be used alone or in combination of two or more. In the case where the adhesive layer 12 is a radiation-curable adhesive layer as described below, the base material 11 is preferably radiolucent.

When the substrate 11 is a plastic film, the plastic film may be unaligned, and may be aligned in at least one direction (uniaxial direction, biaxial direction, etc.). When aligned in at least one direction, the plastic film can be thermally contracted in the at least one direction. If it has heat shrinkability, the outer peripheral portion of the semiconductor wafer of the dicing tape 10 can be thermally shrunk. As a result, the distance between the semiconductor wafers with the single-layered adhesive layer can be fixed in an enlarged state. Therefore, the semiconductor wafer can be easily picked up. In order to make the substrate 11 and the dicing tape 10 have isotropic heat shrinkability, the substrate 11 is preferably a biaxially oriented film. Furthermore, the plastic film aligned in at least one direction can be obtained by extending the unstretched plastic film in the at least one direction (uniaxial extension, biaxial extension, etc.). The heat shrinkage rate in the heat treatment test performed under the conditions of a heating temperature of 100 ° C. and a heating time of 60 seconds for the substrate 11 and the cut crystal strip 10 is preferably 1 to 30%, more preferably 2 to 25%, and more It is preferably 3 to 20%, particularly preferably 5 to 20%. The thermal shrinkage ratio is preferably a thermal shrinkage ratio in at least one of a MD (machine direction) direction and a TD (tranverse direction) direction.

The side surface of the adhesive layer 12 of the base material 11 can also be used for the purpose of improving the adhesion and retention with the adhesive layer 12, and for example, corona discharge treatment, plasma treatment, frosting treatment, ozone exposure treatment, and flame exposure treatment can be performed. Physical treatments such as high-voltage electric shock exposure treatment and ionizing radiation treatment; chemical treatments such as chromic acid treatment; surface treatments such as easy subsequent treatment using a coating agent (primer). In addition, in order to provide antistatic ability, a conductive vapor-deposited layer including a metal, an alloy, an oxide thereof, or the like may be provided on the surface of the substrate 11. The surface treatment for improving the adhesion is preferably performed on the entire surface of the adhesive layer 12 side in the substrate 11.

The thickness of the base material 11 is preferably 40 μm or more, and more preferably 50 from the viewpoint of ensuring the strength of the base material 11 to function as a support in the cut crystal band 10 and the cut crystal sticky film 1. μm or more, more preferably 55 μm or more, and particularly preferably 60 μm or more. Moreover, from the viewpoint of achieving moderate flexibility in the dicing tape 10 and the dicing die-bonding film 1, the thickness of the substrate 11 is preferably 200 μm or less, more preferably 180 μm or less, and even more preferably 150 μm or less.

(Adhesive layer) The adhesive layer 12 in the cut crystal adhesive film 1 may be an adhesive layer that can intentionally reduce the adhesion force due to external effects during the use of the cut crystal adhesive film 1 (adhesive force may be (Reduced adhesive layer), or an adhesive layer (the non-reduced adhesive layer) whose adhesive force is hardly or completely reduced by external action during the use of the cut crystal adhesive film 1 can be It is appropriately selected in accordance with a method or conditions for singulating a semiconductor wafer that is singulated using the die-cutting die-bonding film 1.

In the case where the adhesive layer 12 is an adhesive force-reducible adhesive layer, the state and display of the relatively high adhesive force of the adhesive layer 12 can be displayed during the manufacturing process or use of the cut crystal adhesive film 1 The relatively low adhesion state is used separately. For example, when the adhesive layer 20 is adhered to the adhesive layer 12 of the dicing tape 10 during the manufacturing process of the dicing die-bonding film 1, or when the dicing die-bonding film 1 is used in the dicing step, adhesion can be used. The state of the adhesive layer 12 shows a relatively high adhesive force. Inhibition / prevention of the adherend such as the adhesive layer 20 from rising from the adhesive layer 12. In the step of picking up the semiconductor wafer with the adhesive layer 10, the pick-up can be easily performed by reducing the adhesive force of the adhesive layer 12.

Examples of the adhesive for forming such a pressure-reducible adhesive layer include radiation-curable adhesives and heat-foamable adhesives. As the adhesive for forming the adhesive force-reducible adhesive layer, one type of adhesive may be used, or two or more types of adhesive may be used.

As the radiation-curable adhesive, for example, an adhesive that is hardened by irradiation with electron beam, ultraviolet rays, α-rays, β-rays, γ-rays, or X-rays can be used, and particularly preferably used by irradiation with ultraviolet rays Hardening type of adhesive (ultraviolet curing adhesive).

Examples of the radiation-curable adhesive include the addition of a radiation-polymerizable monomer component or an oligomer component containing a base polymer such as an acrylic polymer and a radiation-polymerizable functional group such as a carbon-carbon double bond. Type radiation hardening adhesive.

The acrylic polymer is a polymer containing a structural unit derived from an acrylic monomer (a monomer component having a (meth) acrylfluorene group in the molecule) as a structural unit of the polymer. It is preferable that the said acrylic polymer is a polymer which contains the structural unit derived from a (meth) acrylate at the most by a mass ratio. The acrylic polymer may be used alone or in combination of two or more.

Examples of the (meth) acrylate include a hydrocarbon group-containing (meth) acrylate. Examples of the hydrocarbon group-containing (meth) acrylate include those exemplified above as the structural unit of the acrylic resin that is a thermoplastic resin that can be contained in the adhesive layer 20. The hydrocarbon group-containing (meth) acrylate may be used alone or in combination of two or more. In order to appropriately express the basic properties such as the adhesiveness obtained by using the hydrocarbon group-containing (meth) acrylate in the adhesive layer 12, the hydrocarbon group-containing (meth) acrylic acid is used to form the total monomer component of the acrylic polymer. The ratio of the ester is preferably 40% by mass or more, and more preferably 60% by mass or more.

The acrylic polymer may contain structural units derived from other monomer components that can be copolymerized with the hydrocarbon group-containing (meth) acrylate for the purpose of improving the cohesive force and heat resistance. Examples of the other monomer component include those exemplified above as the structural unit of the acrylic resin that is the thermoplastic resin that can be contained in the adhesive layer 20. These other monomer components may be used alone or in combination of two or more. In order to appropriately express the basic characteristics such as the adhesiveness obtained by using a hydrocarbon group-containing (meth) acrylate in the adhesive layer 12, the total ratio of the other monomer components in the total monomer component used to form the acrylic polymer It is preferably 60% by mass or less, and more preferably 40% by mass or less.

The acrylic polymer may include a structural unit derived from a polyfunctional monomer that can be copolymerized with a monomer component forming the acrylic polymer in order to form a crosslinked structure in its polymer skeleton. Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl Diethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Epoxy (meth) acrylate (e.g. poly (meth) acrylate glycidyl), polyester (meth) acrylate, (meth) acrylate urethane equal to (meth) acrylic acid in the molecule Monomers of fluorenyl groups and other reactive functional groups. These polyfunctional monomers may be used alone or in combination of two or more. In order to appropriately express the basic properties such as the adhesiveness obtained by using a hydrocarbon group-containing (meth) acrylate in the adhesive layer 12, the ratio of the above-mentioned polyfunctional monomer in the total monomer component of the acrylic polymer is used. It is preferably 40% by mass or less, and more preferably 30% by mass or less.

The acrylic polymer is obtained by polymerizing one or more monomer components including an acrylic monomer. Examples of the polymerization method include solution polymerization, emulsion polymerization, block polymerization, and suspension polymerization.

The mass average molecular weight of the acrylic polymer is preferably 100,000 or more, and more preferably 200,000 to 3 million. If the mass average molecular weight is 100,000 or more, there is a tendency that there are fewer low-molecular-weight substances in the adhesive layer, and contamination of the adhesive layer or semiconductor wafer can be more suppressed.

The adhesive layer 12 or the adhesive forming the adhesive layer 12 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 the low-molecular weight substance in the adhesive layer 12. In addition, the mass average molecular weight of the acrylic polymer can be increased. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a polyol compound (such as a polyphenol compound), an aziridine compound, and a melamine compound. When using a cross-linking agent, the amount used is preferably about 5 parts by mass or less, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the base polymer.

Examples of the radiation-polymerizable monomer component include (meth) acrylic acid urethane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (methyl) Acrylate), dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the radiation-polymerizable oligomer component include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based. The molecular weight is preferably About 100 to 30,000. The content of the above-mentioned radiation-curable monomer component and oligomer component in the radiation-curable adhesive that forms the adhesive layer 12 is, for example, 5 to 500 parts by mass, preferably 40 to 100 parts by mass of the base polymer. ~ 150 parts by mass. In addition, as the additive type radiation-curable adhesive, for example, those disclosed in Japanese Patent Laid-Open No. Sho 60-196956 can be used.

Examples of the radiation-curable adhesive include an inner-pack type of a base polymer containing a functional group such as a polymer side chain or a polymer main chain and a polymerizable carbon-carbon double bond at the end of the polymer main chain. Radiation hardening adhesive. When such an enclosed type radiation-curing adhesive is used, there is a tendency that it is possible to suppress the unanticipated change with time of the adhesive property due to the migration of the low molecular weight components in the formed adhesive layer 12.

As the base polymer contained in the above-mentioned radiation-curable adhesive of the inner type, an acrylic polymer is preferable. Examples of a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer include a method of polymerizing (copolymerizing) a raw material monomer containing a monomer component having a first functional group to obtain an acrylic polymer Then, the compound having a second functional group capable of reacting with the first functional group and a radiation-polymerizable carbon-carbon double bond is subjected to an acrylic polymer under the condition that the radiation-polymerizability of the carbon-carbon double bond is maintained. A condensation reaction or an addition reaction is performed.

Examples of the combination of the first functional group and the second functional group include a carboxyl group and an epoxy group, an epoxy group and a carboxyl group, a carboxyl group and an aziridinyl group, an aziridinyl group and a carboxyl group, and a hydroxyl group and an isocyanate group. , Isocyanate and hydroxyl. Among these, the combination of a hydroxyl group and an isocyanate group, and the combination of an isocyanate group and a hydroxyl group are preferable from a viewpoint of the ease of reaction tracking. Among them, from the viewpoint of ease of production and acquisition of an acrylic polymer having a hydroxyl group, the technical difficulty of producing a polymer having a highly reactive isocyanate group is high. The combination of the first functional group is a hydroxyl group and the second functional group is an isocyanate group. Examples of the compound having an isocyanate group and a radio-polymerizable carbon-carbon double bond, that is, an isocyanate compound containing a radiation-polymerizable unsaturated functional group include, for example, methacrylfluorenyl isocyanate and 2-methyl isocyanate. Propylene ethoxylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc. Examples of the acrylic polymer having a hydroxyl group include monomers derived from the above-mentioned hydroxyl group, or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. Structural units of ether compounds.

The radiation-curable adhesive preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include α-ketohydrin compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, and dibenzenes. Ketone compounds, 9-oxosulfur Compounds, camphorquinone, haloketones, fluorenylphosphine oxide, fluorenyl phosphate and the like. Examples of the α-keto alcohol-based compound include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) one, α-hydroxy-α, α'-dimethylphenethyl Ketones, 2-methyl-2-hydroxyphenylacetone, 1-hydroxycyclohexylphenyl ketone and the like. Examples of the acetophenone-based compound include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl Yl-1- [4- (methylthio) -phenyl] -2-morpholinylpropane-1 and the like. Examples of the benzoin ether-based compound include benzoin diethyl ether, benzoin isopropyl ether, and fennel methyl ether. Examples of the ketal-based compound include benzophenone dimethyl ketal. Examples of the aromatic sulfonyl chloride-based compound include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime-based compound include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Examples of the benzophenone-based compound include benzophenone, benzophenacylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone. As the above 9-oxysulfur Compounds, for example, 9-oxysulfur , 2-chloro9-oxysulfur 2-methyl 9-oxysulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxysulfur , 2,4-dichloro 9-oxysulfur , 2,4-diethyl 9-oxysulfur 2,4-diisopropyl 9-oxysulfur Wait. The content of the photopolymerization initiator in the radiation-curable adhesive is, for example, 0.05 to 20 parts by mass based on 100 parts by mass of the base polymer.

The heat-foamable adhesive is an adhesive containing a component (foaming agent, thermally expandable microspheres, etc.) that expands or expands by heating. Examples of the foaming agent include various inorganic foaming agents and organic foaming agents. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and azides. Examples of the organic foaming agent include chlorochloroalkanes such as trichloromonofluoromethane and dichloromonofluoromethane; and azobisisobutyronitrile, azodimethylformamide, and barium azodicarboxylate. Nitrogen compounds; p-toluenesulfonyl hydrazine, diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis (benzenesulfonylhydrazine), allylbis (sulfonylhydrazine), etc. Hydrazine-based compounds; p-toluenesulfonamide urea, 4,4'-oxybis (benzenesulfonamide) and other amine urea-based compounds; 5-morpholinyl-1,2,3,4-thiatriazole, etc. Triazole compounds; N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroso-p-xylylenediamine and other N-nitroso Base compounds. Examples of the thermally expandable microspheres include microspheres in which a substance which is easily vaporized and expanded by heating is enclosed in a shell. Examples of the substance that can be easily vaporized and expanded by heating include isobutane, propane, and pentane. By encapsulating a substance which is easily vaporized and expanded by heating with a coacervation method or an interfacial polymerization method or the like into a shell-forming substance, thermally expandable microspheres can be produced. As the shell-forming substance, a substance that exhibits thermal melting properties or a substance that can be broken by the action of thermal expansion of the enclosed substance can be used. Examples of such a substance include a vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polyfluorene.

Examples of the non-reduced pressure-sensitive adhesive layer include a pressure-sensitive pressure-sensitive adhesive layer. In addition, the pressure-sensitive adhesive layer includes an adhesive layer in a form in which an adhesive layer formed of the radiation-hardening adhesive described above with respect to the adhesive-reducible adhesive layer is irradiated with radiation in advance. Hardened and has a certain adhesion. As the adhesive for forming the non-reduced adhesive layer, one type of adhesive may be used, or two or more types of adhesive may be used. In addition, the entire adhesive layer 12 may be a non-reduced adhesive layer, or a part thereof may be a non-reduced adhesive layer. For example, when the adhesive layer 12 has a single-layer structure, the whole of the adhesive layer 12 is a non-reduced adhesive layer, or a specific part of the adhesive layer 12 (such as a ring frame sticker) The area with the target area and located outside the central area) is a non-reduced adhesive layer and the other portions (for example, the central area of the area to be attached to the semiconductor wafer) are adhesive-reducible adhesive layers. In addition, in the case where the adhesive layer 12 has a laminated structure, all the adhesive layers in the buildable structure are non-reduced adhesive layers, or a part of the laminated structure is non-reduced adhesive.剂 层。 The agent layer.

Adhesive layer (radiation-curable adhesive layer without radiation) made of a radiation-curable adhesive layer (radiation-curable adhesive layer without radiation) in advance (radiation-curable adhesive layer) Even if the adhesive force is reduced by radiation irradiation, it also shows the adhesiveness due to the polymer component contained, and can exert the minimum required adhesive force of the adhesive layer of the crystalline band in the dicing step and the like. In the case of using a radiation-curable adhesive layer that is irradiated with radiation, in the plane direction of the adhesive layer 12, the entire adhesive layer 12 is a radiation-curable adhesive layer that is irradiated with radiation, and an adhesive layer may also be used. One part of 12 is a radiation-curable adhesive layer that is irradiated with radiation and the other part is a radiation-curable adhesive layer that is not irradiated with radiation. In addition, in this specification, the "radiation-hardening adhesive layer" refers to an adhesive layer formed of a radiation-curable adhesive, and includes a radiation-curable adhesive layer and a radiation-curable adhesive layer without radiation irradiation. This adhesive layer is both a radiation-curable adhesive layer that is hardened by irradiation with radiation and hardened.

As the pressure-sensitive adhesive for forming the pressure-sensitive pressure-sensitive adhesive layer, a known or commonly used pressure-sensitive pressure-sensitive adhesive can be used, and an acrylic pressure-sensitive adhesive or a rubber pressure-sensitive adhesive using an acrylic polymer as a base polymer can be favorably used. In the case where the adhesive layer 12 contains an acrylic polymer as a pressure-sensitive adhesive, the acrylic polymer preferably includes a structural unit derived from a (meth) acrylate as a structural unit having the largest mass ratio. Of polymers. As the acrylic polymer, for example, the acrylic polymer described above as the acrylic polymer that can be contained in the additive-type radiation-curable adhesive can be used.

In addition to the above components, the adhesive layer 12 or the adhesive forming the adhesive layer 12 may be formulated with a well-known or commonly used agent such as a cross-linking accelerator, an adhesion imparting agent, an anti-aging agent, and a colorant (pigment, dye, etc.). Additive for adhesive layer. Examples of the colorant include compounds that are colored by irradiating radiation. When a compound colored by irradiating a radiation is contained, only a portion irradiated with the radiation can be colored. The compound colored by irradiating the radiation is colorless or light-colored before the radiation is irradiated, but the compound is colored by the radiation, and examples thereof include leuco dyes. The amount of the compound to be colored by irradiation with radiation is not particularly limited, and can be appropriately selected.

The thickness of the adhesive layer 12 is not particularly limited. When the adhesive layer 12 is an adhesive layer formed of a radiation-curable adhesive, the adhesive layer 12 is bonded to the adhesive layer 20 before and after the radiation is hardened. From the viewpoint of force balance, it is preferably about 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably 5 to 25 μm.

The cut-crystal die-bonding film 1 may have a separator. Specifically, it may be in the form of a sheet having an isolation film in each of the cut crystal sticky film 1, or the isolation film may be a long strip with a plurality of cut crystal sticky films 1 arranged thereon and isolate the cut film The film is wound to form a roll. The isolation film is an element for covering and protecting the surface of the adhesive layer 20 of the crystalline die-casting film 1 and is peeled from the film when the crystalline die-casting film 1 is used. Examples of the release film include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and a surface coating with a release agent such as a fluorine-based release agent or an acrylic long-chain alkyl ester-based release agent. Cloth plastic film or paper. The thickness of the separator is, for example, 5 to 200 μm.

The cut crystal sticky film 1 according to an embodiment of the cut crystal sticky film of the present invention is manufactured, for example, as follows. First, the substrate 11 can be formed by a known or conventional film-forming method. Examples of the film forming method include a calendering film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a coextrusion method, and a dry lamination method.

Second, an adhesive layer-forming composition (adhesive composition) including an adhesive and a solvent for forming the adhesive layer 12 may be coated on the substrate 11 to form a coating film. The coating film is cured by curing or the like to form the adhesive layer 12. Examples of the coating method include known or commonly used coating methods such as roll coating, screen coating, and gravure coating. The solvent removal conditions can be performed, for example, at a temperature of 80 to 150 ° C. and a time of 0.5 to 5 minutes. Alternatively, after the adhesive composition is coated on the release film to form a coating film, the coating film is cured under the solvent removal conditions described above to form the adhesive layer 12. Thereafter, the adhesive layer 12 and the release film are bonded together on the base material 11. The dicing tape 10 can be produced as described above.

Regarding the adhesive layer 20, first, a composition (adhesive composition) for forming the adhesive layer 20 containing a thermosetting component, a filler, a hardening accelerator, a solvent, and the like is prepared. Next, after the adhesive composition is applied on a release film to form a coating film, the coating film is cured by desolvating or curing, if necessary, to form the adhesive layer 20. The coating method is not particularly limited, and examples thereof include known or conventional coating methods such as roll coating, screen coating, and gravure coating. In addition, as a solvent removal condition, it is performed within the range of the temperature of 70-160 degreeC, and the time of 1-5 minutes, for example.

Then, the self-cutting crystal strip 10 and the adhesive layer 20 are respectively peeled from the release film so that the adhesive layer 20 and the adhesive layer 12 become bonding surfaces, and the two are bonded together. Bonding can be performed, for example, by pressure bonding. In this case, the lamination temperature is not particularly limited, but is preferably 30 to 50 ° C, more preferably 35 to 45 ° C. The linear pressure is not particularly limited, but is preferably 0.1 to 20 kgf / cm, more preferably 1 to 10 kgf / cm.

In the case where the adhesive layer 12 is a radiation-curable adhesive layer as described above, when the adhesive layer 12 is irradiated with radiation such as ultraviolet rays after bonding to the adhesive layer 20, for example, the adhesive layer is faced from the substrate 11 side 12 is irradiated with radiation, and the irradiation dose is, for example, 50 to 500 mJ, and preferably 100 to 300 mJ. The irradiation area (irradiation area R) in the cut crystal adhesive film 1 as the measure for reducing the adhesive force of the adhesive layer 12 (irradiated area R) is generally the area other than the peripheral edge portion of the adhesive layer 20 in the adhesive layer 12 region. In the case where the irradiation area R is locally provided, it may be performed through a mask formed with a pattern corresponding to an area other than the irradiation area R. In addition, a method of irradiating the radiation with dots to form the irradiation region R may be mentioned.

The dicing die-bonding film 1 shown in FIG. 1 can be fabricated as described above.

The die-cut die-bond film 1 can be used in the manufacture of semiconductor devices. Specifically, it is as described in the manufacturing method of a semiconductor device mentioned later. Then, the adhesive layer 20 in the dicing die-bonding film 1 is incorporated into the manufactured semiconductor device. Specifically, it is preferably used for the bonding use of the adherend and the semiconductor wafer and / or the bonding use of the semiconductor wafers to each other, and more preferably as shown in FIGS. 7 (b1), 7 (b2), and 7 (c). As shown in the figure, a semiconductor device (multi-layer laminated semiconductor device) formed by laminating a plurality of stages of a semiconductor wafer is used for bonding an adherend to a semiconductor wafer and / or a bonding application of the semiconductor wafers to each other. As shown in FIGS. 7 (b1), 7 (b2), and 7 (c), the adhesive layer 20 is preferably used for at least overhang portions in a multi-layer laminated semiconductor device having overhang portions.

[Manufacturing Method of Semiconductor Device] A semiconductor device can be manufactured by using the cut-to-seal die-bonding film of the present invention. Specifically, a semiconductor device can be manufactured by a manufacturing method including the following steps: a divided body of a semiconductor wafer including a plurality of semiconductor wafers is attached to the above-mentioned adhesive layer side of the dicing die-bonding film of the present invention, or The step of singulating a semiconductor wafer into a plurality of semiconductor wafers (sometimes referred to as "step A"); under relatively low temperature conditions, extending the dicing tape in the dicing die-bonding film of the present invention, at least cutting the above A step of obtaining a semiconductor wafer with an adhesive layer (sometimes referred to as "step B"); under relatively high temperature conditions, extending the dicing tape to expand the distance between the semiconductor wafers with the adhesive layer A step (sometimes referred to as "step C"); and a step of picking up the above-mentioned semiconductor wafer with an adhesive layer (sometimes referred to as "step D").

The above-mentioned divided body of a semiconductor wafer including a plurality of semiconductor wafers used in step A, or a semiconductor wafer that can be singulated into a plurality of semiconductor wafers can be obtained in the following manner. First, as shown in FIG. 2 (a) and FIG. 2 (b), a dividing groove 30a is formed in the semiconductor wafer W (dividing groove forming step). The semiconductor wafer W includes a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the first surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) necessary for the semiconductor elements have been formed on the first surface Wa. Then, after the wafer processing tape T1 having the adhesive surface T1a is attached to the second surface Wb side of the semiconductor wafer W, the semiconductor wafer W is held on the wafer processing tape T1, and then cut using A rotating blade of a crystal device or the like forms a dividing groove 30a of a specific depth on the first surface Wa side of the semiconductor wafer W. The dividing groove 30a is a space for separating the semiconductor wafer W into semiconductor wafer units (the dividing groove 30a is schematically shown by thick lines in FIGS. 2 to 4).

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

Next, as shown in FIG. 2 (d), the semiconductor wafer W is thinned to a specific thickness by performing a grinding process from the second surface Wb while holding the semiconductor wafer W on the wafer processing tape T2. Thickness (wafer thinning step). The grinding processing can be performed using a grinding processing 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 includes a portion (connection portion) on the second surface Wb side where a portion of the wafer to be singulated into a plurality of semiconductor wafers 31 is connected. 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 front end on the second surface Wb side of the dividing groove 30a is, for example, 1 to 30 μm, and preferably 3 to 20 μm. .

(Step A) In step A, a divided body of a semiconductor wafer containing a plurality of semiconductor wafers or a semiconductor wafer that can be singulated into a plurality of semiconductor wafers is attached to the adhesive layer 20 side of the dicing die-bond film 1. circle.

In one embodiment of step A, as shown in FIG. 3 (a), the semiconductor wafer 30A held on the wafer processing tape T2 is bonded to the adhesive layer 20 of the dicing die-bonding film 1. Thereafter, as shown in FIG. 3 (b), the wafer processing tape T2 is peeled from the semiconductor wafer 30A. In the case where the adhesive layer 12 in the dicing die-bonding film 1 is a radiation-hardening adhesive layer, the adhesive layer can also be faced from the substrate 11 side after the semiconductor wafer 30A is bonded to the adhesive layer 20. 12 is irradiated with radiation such as ultraviolet rays instead of the above-mentioned radiation in the manufacturing process of the cut-to-slice cement film 1. The irradiation dose is, for example, 50 to 500 mJ / cm ² , and preferably 100 to 300 mJ / cm ² . The irradiation area (irradiation area R shown in FIG. 1) where the adhesive force reduction measure of the adhesive layer 12 is performed in the cut crystal adhesive film 1 is, for example, the area within the bonding area of the adhesive layer 20 in the adhesive layer 12. Areas other than the periphery.

(Step B) In step B, the dicing tape 10 in the dicing die-bonding film 1 is extended under a relatively low temperature condition, and at least the adhesive layer 20 is cut to obtain a semiconductor wafer with an adhesive layer.

In one embodiment of step B, first, the ring-shaped frame 41 is attached to the adhesive layer 12 of the dicing tape 10 in the dicing die-casting film 1, as shown in FIG. 4 (a). The dicing die-bond film 1 with the semiconductor wafer 30A attached thereto is fixed on a holder 42 of an extension device.

Next, as shown in FIG. 4 (b), the first stretching step (cold stretching step) under relatively low temperature conditions is performed, the semiconductor wafer 30A is singulated into a plurality of semiconductor wafers 31, and the die-bonding die-bonding film 1 The adhesive layer 20 is then cut into small pieces of the adhesive layer 21 to obtain a semiconductor wafer 31 with the adhesive layer. In the cold-drawing step, the hollow cylindrical shaped jacking member 43 of the extension device is brought into contact with the dicing tape 10 on the lower side of the dicing die-bonding film 1 and raised, so that the semiconductor wafer 30A is bonded. The dicing tape 10 of the dicing die-bonding film 1 extends in a two-dimensional direction including the semiconductor wafer 30A in the radial direction and the circumferential direction. This elongation is performed under the condition that a tensile stress in the range of 15 to 32 MPa, and preferably 20 to 32 MPa is generated in the crystalline band 10. The temperature condition in the cold stretching step is, for example, 0 ° C or lower, preferably -20 to -5 ° C, more preferably -15 to -5 ° C, and even more preferably -15 ° C. The stretching speed (the speed at which the jacking member 43 is raised) in the cold stretching step is preferably 0.1 to 100 mm / sec. The amount of elongation in the cold elongation step is preferably 3 to 16 mm.

In step B, when a semiconductor wafer 30A capable of being singulated into a plurality of semiconductor wafers is used, a cut is made in the semiconductor wafer 30A at a thin-walled and easily broken portion, and the wafer is singulated into the semiconductor wafer 31. At the same time, in step B, in the adhesive layer 20 that is in close contact with the adhesive layer 12 of the extended dicing tape 10, the deformation in the areas in which the semiconductor wafers 31 are in close contact is suppressed. In the vertical direction of the division grooves between the semiconductor wafers 31 in the figure, the tensile stress generated in the dicing tape 10 is applied in a state where such deformation suppression effect is not generated. As a result, a portion in the vertical direction of the division grooves between the semiconductor wafers 31 in the adhesive layer 20 is cut. After the cutting by extension, as shown in FIG. 4 (c), the jacking member 43 is lowered to release the extended state of the dicing tape 10.

(Step C) In step C, under the condition of relatively high temperature, the above-mentioned dicing tape 10 is extended to increase the interval between the semiconductor wafers of the adhesive layer.

In one embodiment of step C, first, as shown in FIG. 5 (a), a second extension step (normal temperature extension step) under relatively high temperature conditions is performed to increase the distance between the semiconductor wafers 31 with the adhesive layer (spaced apart). distance). In step C, the hollow cylinder-shaped jacking member 43 provided in the extension device is raised again to extend the cut band 10 of the cut crystal sticky film 1. The temperature condition in the second stretching step is, for example, 10 ° C or higher, and preferably 15 to 30 ° C. The extension speed (the speed at which the jacking member 43 is raised) in the second extension step is, for example, 0.1 to 10 mm / second, and preferably 0.3 to 1 mm / second. The extension amount in the second extension step is, for example, 3 to 16 mm. In step C, the separation distance of the semiconductor wafer 31 with the adhesive layer is enlarged to such an extent that the semiconductor wafer 31 with the adhesive layer can be appropriately picked from the dicing tape 10 in a pickup step described later. After extending the separation distance by extension, as shown in FIG. 5 (b), the jacking member 43 is lowered to release the extended state of the dicing tape 10. From the viewpoint of suppressing the narrowing of the separation distance of the semiconductor wafer 31 with the adhesive layer on the dicing tape 10 after the stretched state is released, it is preferred that the semiconductors in the dicing tape 10 be made smaller before the extended state is released. The outer portion of the holding area of the wafer 31 is heated to shrink it.

After step C, a cleaning step of washing the semiconductor wafer 31 side of the dicing tape 10 of the semiconductor wafer 31 with the adhesive layer by using a cleaning solution such as water may be optionally performed.

(Step D) In step D (pickup step), a singulated semiconductor wafer with an adhesive layer is picked up. In one embodiment of step D, after the cleaning step is performed as necessary, as shown in FIG. 6, the semiconductor wafer 31 with the adhesive layer is picked from the dicing tape 10. For example, after the pin member 44 of the pick-up mechanism is raised on the lower side of the dicing tape 10 and the semiconductor wafer 31 with the adhesive layer to be picked up is lifted through the dicing tape 10, the suction jig 45 Its adsorption remains. In the picking-up step, the jacking speed of the pin member 44 is, for example, 1 to 100 mm / sec, and the jacking amount of the pin member 44 is, for example, 50 to 3000 μm.

The method for manufacturing the semiconductor device may include steps other than steps A to D. For example, in one embodiment, as shown in FIG. 7 (a), the picked-up semiconductor wafer 31 with the adhesive layer is pre-fixed to the adherend 51 via the adhesive layer 21 (pre-fixing step). Examples of the adherend 51 include a lead frame, a TAB (Tape Automated Bonding) film, a wiring board, and a separately manufactured semiconductor wafer. The shear adhesive force at 25 ° C. during the pre-fixing of the adhesive layer 21 is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa, with respect to the adherend 51. The above-mentioned shear adhesive force of the adhesive layer 21 is 0.2 MPa or more. In the wire bonding step described later, the bonding surface between the adhesive layer 21 and the semiconductor wafer 31 or the adherend 51 due to ultrasonic vibration or heating can be suppressed. Shear deformation occurs, and wire bonding is appropriately performed. Moreover, the shear adhesive force at 175 degreeC at the time of the pre-adhesion of the adhesive layer 21 is 0.01 MPa or more with respect to the to-be-adhered body 51, More preferably, it is 0.01-5 MPa. After the pre-fixing step, the adhesive layer 21 may be heated under conditions of, for example, 130 ° C. for 30 minutes to incompletely harden (pre-curing step).

Next, an electrode pad (not shown) of the semiconductor wafer 31 and a terminal portion (not shown) included in the adherend 51 are electrically connected via a bonding wire 52 (wire bonding step). The connection between the electrode pad of the semiconductor wafer 31 or the terminal portion of the adherend 51 and the bonding wire 52 can be achieved by ultrasonic welding with heating, so that the adhesive layer 21 is not thermally hardened. 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 during wire bonding is, for example, 80 to 250 ° C, and preferably 80 to 220 ° C. The heating time is several seconds to several minutes.

When a configuration is shown in FIG. 7 (b1) in which a semiconductor wafer 31 is laminated in multiple stages on an adherend 51 via an adhesive layer 21, a pre-fixing step and a wire bonding step are performed in the following manner. After the picked-up semiconductor wafer 31 with the adhesive layer is pre-fixed to the adherend 51 via the adhesive layer 21 (FIG. 7 (a)), the semiconductor wafer 31 with the adhesive layer picked up separately is further processed with The above pre-fixing step pre-fixes the upper surface of the semiconductor wafer 31 which has been pre-fixed to the adherend 51 via the adhesive layer 21 in the same manner. In addition, at this time, the pre-fixing is performed while avoiding the electrode pads pre-fixed on the upper surface of the semiconductor wafer 31 of the adherend 51 and staggered in the planar direction. This pre-fixing is repeated several times (pre-fixing step). Thereafter, if necessary, the above-mentioned pre-curing step is performed to incompletely harden the plurality of adhesive layers 21, and then each semiconductor wafer 31 is wire-bonded (wire-bonding step) in the same manner as the wire-bonding step described above.

In the multi-layer laminated structure of the semiconductor wafer 31 as shown in FIG. 7 (b1), the semiconductor wafer 31 with an adhesive layer is used as a unit, and it is in a plane direction so as to avoid the wiring portion (FIG. 7 (b1) The right direction in)) is staggered. In such a multi-layer build-up structure, the uppermost semiconductor wafer 31a is wire-bonded to the overhang portion. In addition, as a multi-stage laminated structure of another form, as shown in FIG. 7 (b2), the multi-stage laminated structure is to prevent the semiconductor wafer 31 from being expanded too far in the planar direction, and the semiconductor wafer 31 with an adhesive layer is used as A unit is laminated in a plane plane direction (such as the right direction), and is layered at a stage of the base layer to a certain degree, and the deviation direction is reversed in another plane direction (such as the left direction). In the multi-layer stack structure of this other form, the uppermost semiconductor wafer 31a and the semiconductor wafer 31b at a portion where the stack direction is reversed are wire-bonded to the overhang portion.

Next, as shown in FIG. 7 (c), the semiconductor wafer 31 is sealed with a sealing resin 53 for protecting each semiconductor wafer 31 or bonding wire 52 on the adherend 51 (sealing step). In the sealing step, heat curing of the adhesive layer 21 is performed. In the sealing step, the sealing resin 53 is formed, for example, by a transfer molding technique using a mold. As a constituent material of the sealing resin 53, for example, an epoxy resin can be used. In the sealing step, a heating temperature for forming the sealing resin 53 is, for example, 165 to 185 ° C., and a heating time is, for example, 60 seconds to several minutes. In the case where the hardening of the sealing resin 53 is not sufficiently performed in the sealing step, a post-hardening step for completely hardening the sealing resin 53 is performed after the sealing step. That is, when the adhesive layer 21 is not completely thermally cured in the sealing step, the adhesive layer 21 and the sealing resin 53 may be completely thermally cured together 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 with the adhesive layer is pre-fixed to the adherend 51, the wire bonding step is performed without completely curing the adhesive layer 21 thermally. Instead of such a configuration, in the above-mentioned method of manufacturing a semiconductor device, the semiconductor wafer 31 with an adhesive layer may be pre-fixed to the adherend 51, the adhesive layer 21 may be thermally cured, and then a wire bonding step may be performed.

In the above-mentioned method for manufacturing a semiconductor device, as another embodiment, instead of the wafer thinning step described above with reference to FIG. 2 (d), the wafer thinning step shown in FIG. 8 may be performed. After the process described above with reference to FIG. 2 (c), in the wafer thinning step shown in FIG. 8, the semiconductor wafer W is maintained in the state of the wafer processing tape T2 by The second surface Wb is subjected to a grinding process to thin the wafer to a specific thickness to form a semiconductor wafer divided body 30B including a plurality of semiconductor wafers 31 and held by the wafer processing tape T2. In the wafer thinning step described above, a method of grinding the wafer until the dividing groove 30a is exposed on the second surface Wb side (the first method), or a method of grinding the wafer from the second surface Wb side until reaching the dividing groove 30a Then, a method of forming a semiconductor wafer divided body 30B by forming a crack between the dividing groove 30a and the second surface Wb by the pressing force of the self-rotating grindstone on the wafer (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, the division groove 30 a after the first method, or the division groove 30 a after the second method, and the cracks connected to the division groove 30 a are schematically shown by thick lines. In the method for manufacturing a semiconductor device described above, in step A, the semiconductor wafer divided body 30B produced in the above manner as a semiconductor wafer divided body may be used instead of the semiconductor wafer 30A. Refer to FIGS. 3 to 7. Steps described in the article.

FIG. 9 (a) and FIG. 9 (b) show step B in this embodiment, that is, the first extension step (cold extension step) performed after the semiconductor wafer split body 30B is bonded to the dicing die-bonding film 1. . In step B in this embodiment, the hollow cylindrical shaped jacking member 43 of the extension device is brought into contact with the cut-off tape 10 on the lower side of the cut-crystal die-bond film 1 in the figure, and raised, so that a semiconductor is bonded. The dicing tape 10 of the dicing die-bonding film 1 of the wafer split body 30B extends in a two-dimensional direction including the semiconductor wafer split body 30B in the radial direction and the circumferential direction. This elongation is performed under the condition that a tensile stress in the range of 5 to 28 MPa, and preferably 8 to 25 MPa is generated in the cut band 10. The temperature condition in the cold drawing step is, for example, 0 ° C or lower, preferably -20 to -5 ° C, more preferably -15 to -5 ° C, and even more preferably -15 ° C. The stretching speed (the speed at which the jacking member 43 is raised) in the cold stretching step is preferably 1 to 400 mm / second. The amount of elongation in the cold elongation step is preferably 50 to 200 mm. Through this cold drawing step, the adhesive layer 20 of the dicing die-bond film 1 is cut into small pieces of the adhesive layer 21 to obtain a semiconductor wafer 31 with an adhesive layer. Specifically, in the cold-drawing step, in the adhesive layer 20 that is in close contact with the adhesive layer 12 of the extended dicing tape 10, the areas in which the semiconductor wafers 31 of the semiconductor wafer segment 30B are in contact are deformed to obtain Suppression, on the other hand, applies tensile stress generated in the dicing tape 10 to the portion in the vertical direction in the drawing of the division grooves 30a between the semiconductor wafers 31 in a state where such deformation suppression is not generated. As a result, a portion in the vertical direction in the drawing of the division groove 30 a between the semiconductor wafers 31 in the adhesive layer 20 is cut.

In the above-mentioned method for manufacturing a semiconductor device, as still another embodiment, a semiconductor wafer 30C produced by the following method 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 on the semiconductor wafer W. The semiconductor wafer W includes a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the first surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) necessary for the semiconductor elements have been formed on the first surface Wa. Then, the wafer processing tape T3 having the adhesive surface T3a is bonded to the first surface Wa side of the semiconductor wafer W, and then the semiconductor wafer W is held in the state of the wafer processing tape T3 to gather the wafers. The laser light with the light spot aligned inside the wafer is irradiated onto the semiconductor wafer W along the predetermined division line from the side opposite to the wafer processing tape T3, and the semiconductor wafer W is formed by the ablation using multiphoton absorption.质 tent 30b. The modified region 30b is a fragile region for separating the semiconductor wafer W into semiconductor wafer units. A method for forming a modified region 30b on a predetermined division line by irradiating with laser light in a semiconductor wafer is described in detail in, for example, Japanese Patent Laid-Open No. 2002-192370, but the laser light in this embodiment The irradiation conditions are appropriately adjusted within a range of the following conditions, for example. ＜ Laser light irradiation conditions ＞ (A) Laser light laser source Semiconductor laser excitation Nd: YAG laser wavelength 1064 nm Laser spot cross-section area 3.14 × 10 ^-8 cm ² Oscillation mode Q switching pulse repetition frequency 100 kHz or less Pulse width Laser light quality TEM00 with output below 1 μs TEM00 Polarization characteristics Linear polarization (B) Condensing lens with magnification of 100 times or less NA 0.55 Transmission of laser light wavelength 100% or less (C) Movement of mounting stage on which semiconductor substrate is placed Speed 280 mm / s or less

Next, as shown in FIG. 10 (c), the semiconductor wafer W is thinned to a specific thickness by performing a grinding process from the second surface Wb while holding the semiconductor wafer W on the wafer processing tape T3. Thus, a semiconductor wafer 30C that can be singulated into a plurality of semiconductor wafers 31 is formed (wafer thinning step). In the method for manufacturing a semiconductor device described above, in step A, a semiconductor wafer 30C fabricated in the above manner as a semiconductor wafer that can be singulated may be used instead of the semiconductor wafer 30A. Refer to FIGS. 3 to 7. Steps described in the article.

FIG. 11 (a) and FIG. 11 (b) show step B in this embodiment, that is, the first stretching step (cold stretching step) performed after the semiconductor wafer 30C is bonded to the dicing die-bonding film 1. In the cold-drawing step, the hollow cylinder-shaped jacking member 43 provided in the extension device abuts on the dicing tape 10 on the lower side of the dicing die-bond film 1 and rises, and the semiconductor wafer 30C is bonded. The dicing tape 10 of the dicing die-bonding film 1 extends in a two-dimensional direction including the semiconductor wafer 30C in the radial direction and the circumferential direction. This elongation is performed under the condition that a tensile stress in the range of 5 to 28 MPa, and preferably 8 to 25 MPa is generated in the cut band 10. The temperature condition in the cold drawing step is, for example, 0 ° C or lower, preferably -20 to -5 ° C, more preferably -15 to -5 ° C, and even more preferably -15 ° C. The stretching speed (the speed at which the jacking member 43 is raised) in the cold stretching step is preferably 1 to 400 mm / second. The amount of elongation in the cold elongation step is preferably 50 to 200 mm. Through this cold drawing step, the adhesive layer 20 of the dicing die-bond film 1 is cut into small pieces of the adhesive layer 21 to obtain a semiconductor wafer 31 with an adhesive layer. Specifically, in the cold-drawing step, a crack is formed in the fragile modified region 30 b in the semiconductor wafer 30C to form a single wafer into the semiconductor wafer 31. At the same time, in the cold-drawing step, in the adhesive layer 20 that is in close contact with the adhesive layer 12 of the extended dicing tape 10, the deformation in the areas in which the semiconductor wafers 31 of the semiconductor wafer 30C are in close contact is suppressed. On the other hand, a tensile stress generated in the dicing tape 10 is applied to a portion located in a vertical direction in the drawing where a crack is formed on the wafer, in a state where such deformation suppression effect is not generated. As a result, a portion in the vertical direction in the drawing of the crack formation portion located between the semiconductor wafers 31 in the adhesive layer 20 is cut.

Moreover, in the above-mentioned method for manufacturing a semiconductor device, the dicing die-bonding film 1 can be used for obtaining a semiconductor wafer with an adhesive layer as described above, but it can also be used to obtain a three-dimensional layer by stacking a plurality of semiconductor wafers. Use of a semiconductor wafer with an adhesive layer when mounted. In such a three-dimensional mounting, a spacer may be interposed between the semiconductor wafers 31 and the adhesive layer 21, or a spacer may not be interposed. [Example]

The following examples illustrate the invention in more detail, but the invention is not limited in any way by these examples.

Example 1 (Production of cut crystal band) In a reaction vessel provided with a condenser tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 parts by mass of 2-ethylhexyl acrylate (2EHA) and 2-hydroxyethyl acrylate were placed. (HEA) 19 parts by mass, 0.4 parts by mass of benzamidine peroxide, and 80 parts by mass of toluene were polymerized in a nitrogen gas stream at 60 ° C. for 10 hours to obtain a solution containing an acrylic polymer A. 1.2 parts by mass of 2-methacryloxyethyl isocyanate (MOI) was added to the solution containing the acrylic polymer A, and an addition reaction was performed at 50 ° C for 60 hours in an air stream to obtain an acrylic system. Polymer A '. Next, 1.3 parts by mass of a polyisocyanate compound (trade name "Coronate L", manufactured by Tosoh Corporation) and a photopolymerization initiator (trade name "Irgacure 184") were added to 100 parts by mass of the acrylic polymer A '. (Manufactured by BASF) 3 parts by mass to produce an adhesive composition A. The obtained adhesive composition A was coated on a surface of a PET-based release film subjected to polysiloxane treatment, and heated at 120 ° C. for 2 minutes to desolvate to form an adhesive layer A having a thickness of 10 μm. Next, this adhesive layer was bonded to an EVA film (made by Gunshi Co., Ltd. with a thickness of 125 μm) as a base material, and stored at 23 ° C. for 72 hours to obtain a cut crystal tape A.

(Production of adhesive layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to make an epoxy resin (trade name "KI-3000 -4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silica filler (trade name" ST-ZL " (Manufactured by Nissan Chemical Industry Co., Ltd., with an average particle diameter of 85 nm) 350 parts by mass (calculated with silica filler), and hardening accelerator (trade name "Curezol 2PHZ-PW", manufactured by Shikoku Chemical Industry Co., Ltd.) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition A having a solid content concentration of 30% by mass. Next, the adhesive composition A was coated on the polysiloxane release surface with a PET release film (thickness: 50 μm) having a surface subjected to polysiloxane release treatment using an applicator to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer A having a thickness (average thickness) of 10 μm was produced on the PET release film.

(Production of cut crystal and sticky film) The PET-based release film was peeled from the cut crystal tape A, and the adhesive layer A was bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, the crystal-cut adhesive film of Example 1 having a laminated structure including a crystal-cut band and an adhesive layer was produced.

Example 2 (Production of an adhesive layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to obtain 100 parts by mass of an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silicon dioxide filler (trade name" MEK -ST-2040 ", manufactured by Nissan Chemical Industry Co., Ltd., with an average particle size of 190 nm, 350 parts by mass (in terms of silicon dioxide filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", Shikoku Chemical Industries, Ltd. Co., Ltd.) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition B having a solid content concentration of 30% by mass. Next, the adhesive composition B was coated on the polysiloxane release surface with a PET release film (thickness: 50 μm) having a surface subjected to polysiloxane release treatment using an applicator to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer B having a thickness (average thickness) of 10 μm was formed on the PET release film.

(Production of cut crystal and sticky film) Peel off the PET-based release film from the cut crystal tape A, and stick the adhesive layer B to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, the crystal-cutting adhesive film of Example 2 having a laminated structure including a crystal-cutting band and an adhesive layer was produced.

Example 3 (Production of Adhesive Layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to make an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silica filler (trade name" SQ -EM1 ", manufactured by Admatechs Co., Ltd., with an average particle diameter of 300 nm, 350 parts by mass (calculated with silica filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", manufactured by Shikoku Chemical Industry Co., Ltd. ) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition C having a solid content concentration of 30% by mass. Next, the adhesive composition C was applied on the polysiloxane release surface (50 μm thickness) of the PET release film (thickness: 50 μm) with the surface subjected to the polysiloxane release treatment to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer C having a thickness (average thickness) of 10 μm was formed on the PET release film.

(Production of cut crystal and sticky film) The PET-based release film is peeled from the cut crystal tape A, and the adhesive layer C is bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, the crystal-cut adhesive film of Example 3 having a laminated structure including a crystal-cut band and an adhesive layer was produced.

Example 4 (Production of Adhesive Layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to make an epoxy resin (trade name " KI-3000-4 ", 115 parts by Todo Chemical Industry Co., Ltd., 115 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silica filler (trade name" MEK -ST-2040 ", manufactured by Nissan Chemical Industry Co., Ltd., with an average particle size of 190 nm, 220 parts by mass (in terms of silicon dioxide filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", Shikoku Chemical Industries, Ltd. Co., Ltd.) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition D having a solid content concentration of 28% by mass. Next, an adhesive composition D was applied on the polysiloxane release surface (with a thickness of 50 μm) of the PET release film (thickness 50 μm) having a surface subjected to the polysiloxane release treatment to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, an adhesive layer D having a thickness (average thickness) of 10 μm was produced on the PET release film.

(Production of cut crystal and sticky film) The PET-based release film was peeled from the cut crystal tape A, and the adhesive layer D was bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, the crystal-cutting adhesive film of Example 4 having a laminated structure including a crystal-cutting band and an adhesive layer was produced.

Example 5 (Production of an adhesive layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to obtain 100 parts by mass of an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silicon dioxide filler (trade name" MEK -ST-2040 ", manufactured by Nissan Chemical Industry Co., Ltd., with an average particle size of 190 nm, 350 parts by mass (in terms of silicon dioxide filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", Shikoku Chemical Industries, Ltd. Co., Ltd.) 1 part by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition E having a solid content concentration of 30% by mass. Next, the adhesive composition E was coated on the polysiloxane release surface with a PET release film (thickness 50 μm) having a surface subjected to a polysiloxane release treatment using an applicator to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer E having a thickness (average thickness) of 10 μm was formed on the PET release film.

(Production of the cut crystal film) The PET-based release film was peeled from the cut crystal tape A, and the adhesive layer E was bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, the crystal-cut adhesive film of Example 5 having a laminated structure including a crystal-cut band and an adhesive layer was produced.

Example 6 (Production of an adhesive layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to make an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silica filler (trade name" SE2050 -MCV ", manufactured by Admatechs Co., Ltd., with an average particle diameter of 500 nm, 350 parts by mass (in terms of silica filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", manufactured by Shikoku Chemical Industry Co., Ltd. ) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition F having a solid content concentration of 30% by mass. Next, the adhesive composition F was coated on the polysiloxane release surface with a PET release film (thickness 50 μm) having a surface subjected to polysiloxane release treatment using an applicator to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, an adhesive layer F having a thickness (average thickness) of 10 μm was formed on the PET release film.

(Production of the cut crystal and sticky film) The PET-based release film is peeled from the cut crystal tape A, and the adhesive layer F is bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner described above, the crystal-cutting adhesive film of Example 6 having a laminated structure including a crystal-cutting band and an adhesive layer was produced.

Example 7 (Production of an adhesive layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to obtain 100 parts by mass of an epoxy resin (trade name " KI-3000-4 ", 440 parts by mass of Toto Chemical Industry Co., Ltd., 440 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silica filler (trade name" MEK -ST-2040 ", manufactured by Nissan Chemical Industry Co., Ltd., with an average particle diameter of 190 nm, 430 parts by mass (calculated with silica filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", Shikoku Chemical Industries, Ltd. Co., Ltd.) was dissolved in 3 parts by mass of methyl ethyl ketone to prepare an adhesive composition G having a solid content concentration of 30% by mass. Next, an adhesive composition G was applied on a polysiloxane release surface (a thickness of 50 μm) of the PET release film (thickness: 50 μm) having a surface subjected to a polysiloxane release treatment using an applicator to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer G having a thickness (average thickness) of 10 μm was formed on the PET release film.

(Production of the cut crystal film) The PET-based release film was peeled from the cut crystal tape A, and the adhesive layer G was bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner described above, the die-bonding film of Example 7 having a laminated structure including a die-cut zone and an adhesive layer was produced.

Comparative Example 1 (Production of Adhesive Layer) 100 parts by mass of an epoxy resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used for 100 parts by mass of an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silicon dioxide filler (trade name" YA050C " -MJF '', manufactured by Admatechs Co., Ltd., with an average particle diameter of 50 nm, 350 parts by mass (in terms of silica filler), and a hardening accelerator (trade name “Curezol 2PHZ-PW”, manufactured by Shikoku Chemical Industry Co., Ltd. ) 2 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition H having a solid content concentration of 30% by mass. Next, the adhesive composition H was applied on the polysiloxane release surface (the thickness of 50 μm) of the PET release film (thickness: 50 μm) with the surface subjected to the polysiloxane release treatment to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer H having a thickness (average thickness) of 20 μm was formed on the PET release film.

(Production of cut crystal and sticky film) The PET-based release film is peeled from the cut crystal tape A, and the adhesive layer H is bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner described above, a crystal-cut adhesive film of Comparative Example 1 having a laminated structure including a crystal-cut band and an adhesive layer was produced.

Comparative Example 2 (Production of Adhesive Layer) 100 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-70L", manufactured by Nagase ChemteX Co., Ltd., and a mass average molecular weight of 900,000) was used to make an epoxy resin (trade name " KI-3000-4 ", 200 parts by mass of Toto Chemical Industry Co., Ltd., 200 parts by mass of phenol resin (trade name" MEHC-7851SS ", manufactured by Meiwa Chemical Co., Ltd.), silicon dioxide filler (trade name" MEK -ST-2040 ", manufactured by Nissan Chemical Industry Co., Ltd., with an average particle size of 190 nm, 350 parts by mass (in terms of silicon dioxide filler), and a hardening accelerator (trade name" Curezol 2PHZ-PW ", Shikoku Chemical Industries, Ltd. Co., Ltd.) was dissolved in 0.5 parts by mass of methyl ethyl ketone to prepare an adhesive composition I having a solid content concentration of 30% by mass. Next, an adhesive composition I was applied on the polysiloxane release surface (the thickness of 50 μm) of the PET release film (thickness: 50 μm) with the surface subjected to the polysiloxane release treatment to form a coating film. The membrane was desolvated at 120 ° C for 2 minutes. As described above, the adhesive layer I having a thickness (average thickness) of 10 μm was produced on the PET release film.

(Production of cut crystal and sticky film) The PET-based release film was peeled from the cut crystal tape A, and the adhesive layer I was bonded to the exposed adhesive layer. In the bonding, the center of the dicing tape is aligned with the center of the viscous film. For the bonding system, a hand pressure roller is used. Next, the adhesive layer in the dicing tape is irradiated with ultraviolet rays from the EVA substrate side. In the ultraviolet irradiation, a high-pressure mercury lamp was used, and the cumulative light intensity was set to 300 mJ / cm ² . In the manner as described above, a crystal die-bonding film of Comparative Example 2 having a laminated structure including a crystal die zone and an adhesive layer was produced.

<Evaluation> The following evaluations were performed with respect to the adhesive layer and the die-cut adhesive film obtained in the Example and the comparative example. The results are shown in Table 1.

(Exothermic heat before heating) Regarding the adhesive layers obtained in the examples and comparative examples, 10 to 15 mg of the adhesive layer was weighed as a measurement sample, and a differential scanning calorimeter (brand name "Q200", TA Instruments) was used. (Manufactured), the measurement sample was heated from 0 ° C to 350 ° C at a temperature increase rate of 10 ° C / min, and DSC measurement was performed to calculate the total heat generation amount [J / g] at this time as the heat generation amount before heating.

(Exothermic heat after heating at 130 ° C for 30 minutes) Regarding the adhesive layers obtained in Examples and Comparative Examples, the adhesive layers were laminated so as to have a thickness of 200 μm, and the temperature was raised from room temperature in a pressure oven for 30 minutes. To 130 ° C and held at 130 ° C for 30 minutes. In addition, during heating, pressurization was performed using a gas of 7 kgf. Except using the adhesive layer after overheating in this way, the heat generation amount [J / g] after heating at 130 ° C. for 30 minutes was calculated in the same manner as in the “heat generation amount before heating”.

(Storage Elastic Modulus) Regarding the adhesive layers obtained in the examples and comparative examples, the adhesive layers were laminated so as to have a thickness of 200 μm, and the adhesive layer was laminated with the "Exothermic heat after heating at 130 ° C for 30 minutes". Heating and pressing are performed in the same way as heating, and the obtained sample is cut into a strip shape with a width of 4 mm and a length of 30 mm by a cutting knife as a test piece, and a solid viscoelasticity measuring device (measurement device: RSA-G2) is used. , Manufactured by Rheometric Scientific), under the conditions of frequency 1 Hz, heating rate 10 ° C / min, initial chuck distance 10 mm, and strain 0.1%, the dynamic storage is measured in the temperature range of 0 to 200 ° C using a tensile mode Modulus of elasticity. The temperature rise was started after holding at 0 ° C for 5 minutes. Then, the value at 130 ° C was read and this value was taken as the storage elastic modulus [MPa] at 130 ° C after heating at 130 ° C for 30 minutes.

(Average particle diameter of filler) Each of the adhesive layers obtained in Examples and Comparative Examples was thermally cured at 175 ° C for 1 hour, and was embedded in a resin using an EpoFix kit manufactured by Struers. The embedded resin was mechanically polished to expose the cross-section of the adhesive layer, and the cross-section was subjected to ion polishing using a CP processing device (trade name "SM-09010", manufactured by Nippon Electronics Co., Ltd.), and then conductive was performed. Process and observe with FE-SEM. The FE-SEM observation is performed at an acceleration voltage of 1 to 5 kV, and a reflected electron image is observed. Use the image analysis software "Image-J" to identify the filler particles by binarizing the captured images. Divide the area of the filler in the image by the number of fillers in the image to find the average filler. Area, and calculate the average particle diameter of the filler.

(Wafer Lamination Evaluation) An adhesive layer F having a thickness of 25 μm was prepared in the same manner as in Example 6 as an adhesive sheet. This adhesive sheet was bonded to a mirror wafer on which a modified region was formed on a predetermined division line by irradiation with laser light. After curing at 175 ° C for 2 hours, grinding was performed from the mirror wafer side until the mirror wafer and the adhesive sheet were bonded. The total thickness becomes 50 μm. After the wafers and wafers (the wafer bonding temperature: 50-80 ° C) were bonded to the wafers and wafers that were obtained in the examples and comparative examples, a die separator was used. ) (Trade name "DDS2300", manufactured by DISCO Corporation) The wafer is cut and the dicing tape is heat-shrinked to obtain a sample. That is, first, the wafer is cut by using a cold drawing unit under the conditions of an extension temperature of -15 ° C, an extension speed of 100 mm / sec, and an extension amount of 12 mm. The size of the wafer obtained after the cutting was 10 mm × 10 mm, and the thickness of the wafer was 25 μm. Thereafter, the crystalline band was thermally contracted under the conditions of an extension amount of 10 mm, a heating temperature of 250 ° C, an air volume of 40 L / min, a heating distance of 20 mm, and a rotation speed of 3 ° / sec to obtain an adhesive layer. Evaluation wafer.

The wafer for evaluation of the above-mentioned adhesive layer was bonded to a die bonder (trade name "Sticky Bonder SPA-300", manufactured by Shinkawa Co., Ltd.) at a stage temperature of 90 ° C, a load of 1000 gf, and a sticky time 1 Five seconds were laminated on a BGA (Ball Grid Array) substrate (material: AUS308) in a stepwise manner to adhere the crystals. The laminations are formed in a staircase shape by being staggered by 200 μm in the same direction. After lamination, evaluation was performed with the case of no peeling being 0, the case of peeling at one place as △, and the case of peeling at two or more places.

(Evaluation of wire bonding) A wafer having a thickness of 30 μm was obtained by grinding a wafer on which one surface was subjected to aluminum vapor deposition. The wafer for dicing was attached to the adhesive layer side of the dicing die-bond film obtained in the examples and comparative examples, and then the wafer was cut in the same manner as in the "wafer stack evaluation" above to obtain an adhesive Layer of wafer. Five wafers with the adhesive layer obtained were laminated in a stepwise manner on a Cu lead frame under the conditions of a stage temperature of 90 ° C., a gluing load of 1000 gf, and a gluing time of 1 second. The laminations are formed in a staircase shape by being staggered by 200 μm in the same direction. The laminated body after the die-bonding was heated and hardened at 130 ° C for 30 minutes, and a wire bonding device (trade name "Maxum Plus", manufactured by Kulicke & Soffa) was used to bond five wire diameters 18 to the overhang portion of the top wafer μm Au line. The Au wire was hit on a Cu lead frame with an output of 80 Amp, a time of 10 ms, and a load of 50 g. An Au wire was punched on the wafer at a temperature of 130 ° C, an output of 125 Amp, a time of 10 ms, and a load of 80 g. A case where one or more of the five Au wires could not be bonded to the wafer was judged as X, and a case where five of the five Au wires could be joined to the wafer was judged as ○.

(Preservability evaluation) Preservability evaluation was performed by a change in viscosity over time. The viscosity at 90 ° C of the initial stage of the adhesive layer obtained in the examples and the comparative examples after production was used as the initial viscosity, and the viscosity at 90 ° C of the adhesive layer after storage at 23 ° C for 28 days after calculation was compared. Initial viscosity increase rate (viscosity increase rate) [{viscosity at 90 ° C (Pa · s) after storage at 23 ° C for 28 days-initial viscosity (Pa · s)} / initial viscosity (Pa · s) × 100] (%). The case where the viscosity increase rate is less than 100% is regarded as 0, the case where 100% or more and less than 150% is regarded as △, and the case where 150% or more is regarded as ×. The viscosity is measured with a rotary viscometer (trade name "HAAKE MARS III", manufactured by Thermo Fisher Scientific). The measurement conditions were set to a gap of 100 μm, a turntable diameter of 8 mm, a heating rate of 10 ° C./min, a strain of 10%, and a frequency of 5 rad / sec.

◎ [Table 1]

It is shown that the adhesive layer of Examples 1 to 7 has a small increase rate in viscosity and excellent storage stability. Compared with Comparative Examples 1 and 2, the amount of heat generated after heating is smaller than that of Comparative Examples 1 and 2, and can be cured in a short time. And the modulus of elasticity is higher at 130 ° C after hardening, and proper wire bonding can be performed even on the overhang portion.

1‧‧‧ cut crystal film

10‧‧‧ cut crystal ribbon

11‧‧‧ Substrate

12‧‧‧ Adhesive layer

20‧‧‧ Adhesive layer

21‧‧‧ Adhesive layer

30a‧‧‧ split groove

30A‧‧‧Semiconductor wafer

30b‧‧‧Modified area

30B‧‧‧Semiconductor Wafer Split

30C‧‧‧Semiconductor wafer

31‧‧‧semiconductor wafer

31a‧‧‧Semiconductor wafer

31b‧‧‧Semiconductor wafer

41‧‧‧ ring frame

42‧‧‧ holder

43‧‧‧ jacking member

44‧‧‧pin member

45‧‧‧Adsorption fixture

51‧‧‧ Bedding

52‧‧‧ bonding wire

53‧‧‧sealing resin

R‧‧‧ Irradiated area

T1‧‧‧ Wafer Processing Tape

T1a‧‧‧ Adhesive surface

T2‧‧‧ Wafer Processing Tape

T2a‧‧‧ Adhesive surface

T3‧‧‧ Wafer Processing Tape

T3a‧‧‧ Adhesive surface

W‧‧‧Semiconductor wafer

Wa‧‧‧Part 1

Wb‧‧‧Part 2

FIG. 1 is a schematic cross-sectional view showing an embodiment of a cut-to-slice adhesive film according to the present invention. FIGS. 2 (a) to 2 (d) show a part of the steps in a method for manufacturing a semiconductor device using the dicing die-bonding film shown in FIG. 1. 3 (a) and 3 (b) show steps following the step shown in FIG. 4 (a) to (c) show steps following the step shown in FIG. 5 (a) and 5 (b) show steps subsequent to the step shown in FIG. FIG. 6 shows steps following the step shown in FIG. 5. 7 (a), (b1), (b2), and (c) show steps following the step shown in FIG. FIG. 8 shows part of the steps in a modification example of the method of manufacturing a semiconductor device using the die-cut die-bond film shown in FIG. 1. FIGS. 9 (a) and 9 (b) show some steps in a modified example of a method for manufacturing a semiconductor device using the die-cut die-bond film shown in FIG. 1. FIG. FIGS. 10 (a) to (c) show some steps in a modified example of a method of manufacturing a semiconductor device using the die-cut die-bond film shown in FIG. 1. FIGS. 11 (a) and 11 (b) show some steps in a modified example of a method of manufacturing a semiconductor device using the die-cut die-bond film shown in FIG. 1.

Claims (4)

A cut crystal sticky film comprising: a cut crystal tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer peelably and tightly adhered to the above-mentioned adhesive layer in the cut crystal tape; and The adhesive layer contains a thermosetting component, a filler, and a hardening accelerator. The heat generation measured by DSC after heating at 130 ° C for 30 minutes is 60% or less of the heat generation before heating, and at 130 ° C after heating. The storage elastic modulus is above 20 MPa and below 4000 MPa. The crystal-cutting adhesive film of claim 1, wherein the thermosetting component is a thermosetting resin and / or a thermoplastic resin containing a thermosetting functional group. For example, the cut crystal adhesive film of claim 1 or 2, wherein the viscosity of the above adhesive layer at 300 ° C is 300 to 100,000 Pa · s. For example, the cut crystal and sticky film of claim 1 or 2, wherein the filler is silicon dioxide having an average particle diameter of 70 to 300 nm.