JP2017092296A - Dicing/die-bonding film, and method of manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dicing/die-bonding film comprising a thermosetting die-bonding film that is appropriately broken by tensile stress under a low temperature, and that can prevent scattering caused by being broken at an unintended position, and to provide a method of manufacturing a semiconductor device.SOLUTION: Provided is dicing/die-bonding film configured by laminating a thermosetting die-bonding film on a dicing film obtained by laminating an adhesive layer on a base material. A crosslinking index at 0°C of the thermosetting die-bonding film before thermosetting is equal to or more than 0.8 and equal to or less than 4.0.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a dicing die-bonding film and a method for manufacturing a semiconductor device.

  2. Description of the Related Art Conventionally, in a semiconductor device manufacturing process, a dicing die-bonding film has been proposed that adheres and holds a semiconductor wafer in a dicing process and also provides an adhesive layer for chip fixation necessary for a mounting process (for example, Patent Documents). 1). This dicing die-bonding film is obtained by providing an adhesive layer on a dicing film having a supporting base and an adhesive layer, and dicing the semiconductor wafer with a blade while holding the adhesive layer (so-called blade dicing). ) And then expanding the dicing film in the expanding step, and then picking up the separated chips together with the adhesive layer, individually collecting them and attaching the adherend such as a lead frame through the adhesive layer. It is made to adhere to.

  In the case of blade dicing, it is necessary to cut the thermosetting die bond film together with the semiconductor wafer. However, in a general dicing method using a diamond blade, adhesion between a thermosetting die-bonding film and a dicing film due to the influence of heat generated during dicing, adhesion of semiconductor chips due to generation of cutting waste, to the side of the semiconductor chip In the case of thin semiconductor wafers, chipping and the like are concerned, so it is necessary to slow down the cutting speed, resulting in an increase in cost.

  Therefore, in recent years, a method of obtaining individual semiconductor chips by forming grooves on the surface of a semiconductor wafer and then performing back surface grinding (hereinafter also referred to as “DBG (Dicing Before Grinding) method”); for example, Patent Document 2 The semiconductor wafer can be easily divided on the planned dividing line by irradiating the laser beam onto the planned dividing line in the semiconductor wafer, and then the semiconductor wafer can be divided by applying tensile stress. There has been proposed a method (hereinafter also referred to as “stealth dicing (registered trademark)”) of breaking a wafer to obtain individual semiconductor chips (see, for example, Patent Document 3 and Patent Document 4). According to these methods, it is possible to reduce the occurrence of defects such as chipping particularly when the thickness of the semiconductor wafer is thin, and the kerf width (cut white) is made narrower than before. It is said that the yield of semiconductor chips can be improved.

JP 2008-218571 A JP 2003-007649 A JP 2002-192370 A JP 2003-338467 A

  In order to obtain individual semiconductor chips with thermosetting die-bonding film by DBG method or stealth dicing while holding the thermosetting die-bonding film, break the thermosetting die-bonding film together with the semiconductor wafer by tensile stress in the expanding process. There is a need. Therefore, in the DBG method and stealth dicing, a method of expanding at a low temperature (for example, 0 ° C.) is being proposed in order to improve the breakability of the thermosetting die-bonding film. However, when a conventional thermosetting die bond film is expanded at a low temperature, the semiconductor wafer or the thermosetting die bond film is not partially broken, or the thermosetting die bond film is broken at an unintended location. Has been generated, resulting in a reduction in the yield of semiconductor device manufacturing.

  The present invention has been made in view of the above-mentioned problems, and the object thereof is to provide a thermosetting die-bonding film that can be suitably broken by tensile stress at low temperatures and can prevent scattering due to breakage at unintended locations. A dicing die-bonding film and a semiconductor device manufacturing method are provided.

  The inventors of the present application have intensively studied paying attention to the properties at low temperatures of the thermosetting die-bonding film in order to solve the above problems, and as a result, the present invention has been completed.

That is, the present invention is a dicing die bond film in which a thermosetting die bond film is laminated on a dicing film in which an adhesive layer is laminated on a substrate,
It is related with the dicing die-bonding film whose crosslinking index in 0 degreeC of the said thermosetting type die-bonding film before thermosetting is 0.8-4.0.

  In the dicing die-bonding film, since the crosslinking index at 0 ° C. of the thermosetting die-bonding film before thermosetting is 0.7 or more and 4.0 or less, the breakability due to tensile stress at low temperature is good, Scattering due to breakage at an unintended location can be prevented, and the manufacturing yield of the semiconductor device can be improved. If the crosslinking index is less than the above lower limit, the thermosetting die-bonding film becomes so elastic that it breaks at unintended locations and the fragments may scatter. On the other hand, when the crosslinking index exceeds the upper limit, the elasticity of the thermosetting die-bonding film becomes too low and a kind of viscosity (or flexibility) is generated, and the breakability at low temperatures may be lowered.

  It is preferable that the thermosetting die-bonding film has a cross-linking index of 13000 or less at 250 ° C. after the thermosetting die-bonding film is cured by heating at 175 ° C. for 1 hour. When the cross-linking index at 250 ° C. of the thermosetting die-bonding film after thermosetting is in the above range, it is possible to suppress a decrease in elasticity at a high temperature of the thermosetting die-bonding film, and to improve heat reflow resistance. Can do.

  It is preferable that the elongation at break at 0 ° C. of the thermosetting die-bonding film before thermosetting is 5% or more and 500% or less. Thereby, the breakability in the low temperature of a thermosetting type die-bonding film can be made favorable.

  It is preferable that the breaking elongation F1 at 0 ° C. of the dicing film and the breaking elongation F2 at 0 ° C. of the thermosetting die-bonding film before thermosetting satisfy the relationship of F1> F2. Thereby, it is possible to prevent the thermosetting die-bonding film from excessively following the expansion of the dicing film during the expansion, and the thermosetting die-bonding film can be favorably broken.

  It is preferable that the crosslinking index E1 at 0 ° C. of the dicing film and the crosslinking index E2 at 0 ° C. of the thermosetting die-bonding film before thermosetting satisfy the relationship of E1> E2. Thereby, the elasticity of the thermosetting die-bonding film at a low temperature can be made higher than the elasticity of the dicing film. In other words, the flexibility or viscosity of the thermosetting die-bonding film at a low temperature can be reduced. The state can be made lower than the viscosity, and the breakability of the thermosetting die-bonding film at a low temperature can be further improved.

Further, the present invention is a method of manufacturing a semiconductor device using the dicing die bond film,
Irradiating laser beam to the division line of the semiconductor wafer to form a modified region on the division line; and
Bonding the semiconductor wafer after the modified region formation to the dicing die-bonding film;
By applying a tensile stress to the dicing die bond film at −30 ° C. to 20 ° C., the semiconductor wafer and the thermosetting die bond film constituting the dicing die bond film are broken at the division line. And forming a semiconductor element;
Picking up the semiconductor element together with the thermosetting die-bonding film;
And a step of die-bonding the picked-up semiconductor element to an adherend via the thermosetting die-bonding film.

The present invention is a method for manufacturing a semiconductor device using the dicing die-bonding film,
Forming a groove on the surface of the semiconductor wafer that does not reach the back surface;
Grinding the back surface of the semiconductor wafer and exposing the groove from the back surface;
Bonding the semiconductor wafer with the groove exposed from the back surface to the dicing die-bonding film;
Under the conditions of −30 ° C. to 20 ° C., by applying a tensile stress to the dicing die bond film, breaking the thermosetting die bond film constituting the dicing die bond film, and forming a semiconductor element;
Picking up the semiconductor element together with the thermosetting die-bonding film;
And a step of die-bonding the picked-up semiconductor element to an adherend via the thermosetting die-bonding film.

  In any of the production methods, since the dicing die-bonding film including the thermosetting die-bonding film having good low-temperature rupture property is used, the thermosetting die-bonding film is suitably broken even under a tensile stress under a low temperature. In addition, the thermosetting die-bonding film can be prevented from breaking and scattering at unintended locations, and the manufacturing efficiency of the semiconductor device can be improved.

It is a cross-sectional schematic diagram which shows the dicing die-bonding film which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram which shows the dicing die-bonding film which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating one manufacturing method of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating one manufacturing method of the semiconductor device which concerns on this embodiment. (A), (b) is a cross-sectional schematic diagram for demonstrating one manufacturing method of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating one manufacturing method of the semiconductor device which concerns on this embodiment. (A) And (b) is a cross-sectional schematic diagram for demonstrating the other manufacturing method of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the other manufacturing method of the semiconductor device which concerns on this embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. However, in some or all of the drawings, parts unnecessary for the description are omitted, and there are parts shown enlarged or reduced for easy explanation. Unless otherwise stated, terms indicating the positional relationship such as up and down are merely used for ease of explanation and are not intended to limit the configuration of the present invention.

<< First Embodiment >>
<Dicing die bond film>
The dicing die bond film of the present invention will be described below. FIG. 1 is a schematic cross-sectional view showing a dicing die-bonding film according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a dicing die-bonding film according to another embodiment of the present invention.

  As shown in FIG. 1, the dicing die bond film 10 has a configuration in which a thermosetting die bond film 3 is laminated on a dicing film 11. The dicing film 11 is configured by laminating the pressure-sensitive adhesive layer 2 on the substrate 1, and the thermosetting die-bonding film 3 is provided on the pressure-sensitive adhesive layer 2. Further, the present invention may have a configuration in which a thermosetting die-bonding film 3 ′ is formed only on a semiconductor wafer attaching portion, like a dicing die-bonding film 12 shown in FIG. 2.

(Dicing film)
The base material 1 preferably has ultraviolet transparency, and serves as a strength matrix for the dicing die bond films 10 and 12. For example, polyolefins such as low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, ethylene-acetic acid Vinyl copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyphenylsulfur De, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), paper, and the like.

  Moreover, as a material of the base material 1, polymers, such as the crosslinked body of the said resin, are mentioned. The plastic film may be used unstretched or may be uniaxially or biaxially stretched as necessary. According to the resin sheet to which heat shrinkability is imparted by stretching treatment or the like, the adhesive area between the pressure-sensitive adhesive layer 2 and the thermosetting die-bonding films 3 and 3 ′ is reduced by thermally shrinking the substrate 1 after dicing. The recovery of the semiconductor chip (semiconductor element) can be facilitated.

  The surface of the substrate 1 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers. Alternatively, a physical treatment or a coating treatment with a primer (for example, an adhesive substance described later) can be performed. The base material 1 can be used by appropriately selecting the same kind or different kinds, and a blend of several kinds can be used as necessary. Further, in order to impart antistatic ability to the base material 1, a conductive material vapor deposition layer having a thickness of about 30 to 500 mm made of metal, alloy, oxides thereof, or the like is provided on the base material 1. be able to. The substrate 1 may be a single layer or two or more types.

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

  The pressure-sensitive adhesive layer 2 preferably includes an ultraviolet curable pressure-sensitive adhesive. The UV curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation of ultraviolet light, and only the portion 2a corresponding to the semiconductor wafer attachment portion of the pressure-sensitive adhesive layer 2 shown in FIG. By irradiating with ultraviolet rays, a difference in adhesive strength with the other portion 2b can be provided.

  Further, by curing the ultraviolet curable pressure-sensitive adhesive layer 2 in accordance with the thermosetting die-bonding film 3 ′ shown in FIG. 2, the portion 2 a having a significantly reduced adhesive force can be easily formed. Since the thermosetting die-bonding film 3 ′ is attached to the portion 2 a that has been cured and has reduced adhesive strength, the interface between the portion 2 a of the pressure-sensitive adhesive layer 2 and the thermosetting die-bonding film 3 ′ is easily peeled off during pick-up. Has properties. On the other hand, the portion not irradiated with ultraviolet rays has a sufficient adhesive force, and forms the portion 2b.

  As described above, in the pressure-sensitive adhesive layer 2 of the dicing die-bonding film 10 shown in FIG. 1, the portion 2b formed of the uncured ultraviolet-curing pressure-sensitive adhesive adheres to the thermosetting die-bonding film 3, and dicing is performed. It is possible to secure a holding force when performing. As described above, the ultraviolet curable pressure-sensitive adhesive can support the thermosetting die-bonding film 3 for die-bonding a semiconductor chip to an adherend such as a substrate with a good balance of adhesion and peeling. In the pressure-sensitive adhesive layer 2 of the dicing die-bonding film 12 shown in FIG. 2, the portion 2b can fix the wafer ring.

  As the ultraviolet curable pressure-sensitive adhesive, those having an ultraviolet curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. Examples of the ultraviolet curable pressure-sensitive adhesive include an additive-type ultraviolet curable pressure-sensitive adhesive in which an ultraviolet curable monomer component or an oligomer component is blended with a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive. Can be illustrated.

  As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer from the viewpoint of cleanability with an organic solvent such as ultrapure water or alcohol of an electronic component that is difficult to contaminate a semiconductor wafer or glass Is preferred.

  Examples of the acrylic polymer include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester , Octadecyl esters, eicosyl esters, etc., alkyl groups having 1 to 30 carbon atoms, especially 4 to 18 carbon linear or branched alkyl esters, etc.) and Meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, acrylic polymers such as one or more was used as a monomer component of the cyclohexyl ester etc.). In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) of the present invention has the same meaning.

The acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. You may go out. Examples of such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate,
Hydroxyl group-containing monomers such as (meth) acrylic acid 12-hydroxylauryl, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid Sulfonic acid group-containing monomers such as (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; acrylamide, acrylonitrile, etc. Is mentioned. One or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total monomer components.

  Furthermore, since the acrylic polymer is crosslinked, a polyfunctional monomer or the like can be included as a monomer component for copolymerization, if necessary. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less of the total monomer components from the viewpoint of adhesive properties.

  The acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization. The polymerization can be performed by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, the content of the low molecular weight substance is preferably small. From this point, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3,000,000.

  In addition, an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them. When using an external cross-linking agent, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, 5 parts by weight or less is preferable with respect to 100 parts by weight of the base polymer. Moreover, it is preferable that it is 0.1 weight part or more as a lower limit. Furthermore, additives such as various tackifiers and anti-aging agents may be used for the adhesive, if necessary, in addition to the above components.

  Examples of the ultraviolet curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta. Examples include erythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the ultraviolet curable oligomer component include urethane, polyether, polyester, polycarbonate, and polybutadiene oligomers, and those having a molecular weight in the range of about 100 to 30000 are suitable. The blending amount of the ultraviolet curable monomer component and oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer. Generally, the amount is, for example, about 5 to 500 parts by weight, preferably about 70 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

  In addition to the additive-type UV-curable pressure-sensitive adhesive described above, the UV-curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain, main chain, or main chain terminal as a base polymer. Intrinsic ultraviolet curable pressure sensitive adhesives using Intrinsic UV curable pressure-sensitive adhesive does not need to contain an oligomer component or the like, which is a low molecular weight component, or does not contain much, so that the oligomer component or the like does not move through the pressure-sensitive adhesive over time and is stable. It is preferable because an adhesive layer having a layer structure can be formed.

  As the base polymer having a carbon-carbon double bond, those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, those having an acrylic polymer as a basic skeleton are preferable. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.

  The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design. . For example, after a monomer having a functional group is previously copolymerized with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into an ultraviolet curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.

  Examples of combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction. Moreover, the functional group may be on either side of the acrylic polymer and the compound as long as the acrylic polymer having the carbon-carbon double bond is generated by a combination of these functional groups. In the preferable combination, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, those obtained by copolymerizing the above-exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.

As the intrinsic ultraviolet curable pressure-sensitive adhesive, the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the ultraviolet curable monomer does not deteriorate the characteristics. Components and oligomer components can also be blended. The UV-curable oligomer component or the like is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the base polymer.

The ultraviolet curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropio Α-ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-
Acetophenone compounds such as [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; Aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3, Benzophenone compounds such as 3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4- Examples include thioxanthone compounds such as dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate. The compounding quantity of a photoinitiator is about 0.05-20 weight part with respect to 100 weight part of base polymers, such as an acryl-type polymer which comprises an adhesive.

  Examples of the ultraviolet curable pressure-sensitive adhesive include photopolymerizable compounds such as addition polymerizable compounds having two or more unsaturated bonds and alkoxysilanes having an epoxy group disclosed in JP-A-60-196956. And a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive containing a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine, and an onium salt-based compound.

  Examples of the method for forming the portion 2a on the pressure-sensitive adhesive layer 2 include a method in which after the ultraviolet curable pressure-sensitive adhesive layer 2 is formed on the substrate 1, the portion 2a is partially irradiated with ultraviolet rays to be cured. . The partial ultraviolet irradiation can be performed through a photomask on which a pattern corresponding to the portion 3b other than the semiconductor wafer bonding portion 3a is formed. Moreover, the method etc. of irradiating and hardening | curing an ultraviolet-ray spotly are mentioned. The ultraviolet curable pressure-sensitive adhesive layer 2 can be formed by transferring what is provided on the separator onto the substrate 1. Partial UV curing can also be performed on the UV curable pressure-sensitive adhesive layer 2 provided on the separator.

  In the pressure-sensitive adhesive layer 2 of the dicing die-bonding film 10, a part of the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays so that (the adhesive strength of the portion 2a) <(the adhesive strength of the other portion 2b). Also good. That is, after forming the ultraviolet-curing pressure-sensitive adhesive layer 2 on the substrate 1, at least one side of the substrate 1 is shielded from all or part of the portion other than the portion corresponding to the semiconductor wafer pasting portion 3 a. By irradiating with ultraviolet rays, the portion corresponding to the semiconductor wafer pasting portion 3a can be cured to form the portion 2a with reduced adhesive strength. As a light shielding material, what can become a photomask on a support film can be produced by printing or vapor deposition. Thereby, the dicing die-bonding film 10 of this invention can be manufactured efficiently.

  The thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, but is preferably about 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably, from the viewpoint of chipping prevention of the chip cut surface and compatibility of fixing and holding of the adhesive layer. 5 to 25 μm.

(Thermosetting die bond film)
The crosslinking index at 0 ° C. of the thermosetting die-bonding films 3 and 3 ′ before thermosetting is 0.8 or more and 4.0 or less. The crosslinking index is preferably 1.0 or more and 4.0 or less, and more preferably 1.2 or more and 3.8 or less. By setting the cross-linking index at 0 ° C. of the thermosetting die-bonding film before thermosetting to the above range, it is possible to prevent breakage due to tensile stress at low temperatures and to prevent scattering due to breakage at unintended locations. Thus, the manufacturing yield of the semiconductor device can be improved. If the crosslinking index is less than the above lower limit, the thermosetting die-bonding film becomes so elastic that it breaks at unintended locations and the fragments may scatter. On the other hand, when the crosslinking index exceeds the upper limit, the elasticity of the thermosetting die-bonding film becomes too low and a kind of viscosity (or flexibility) is generated, and the breakability at low temperatures may be lowered.

The crosslinking index is determined by the following formula.
Cross-linking index (cm ³ / mol) = 3RT / E ′
(In the formula, E ′ is a storage elastic modulus [Pa], R is a gas constant (= 8.31 J / mol · K), and T is an absolute temperature [K].)

  The thermosetting die-bonding film 3, 3 ′ is cured by heat treatment at 175 ° C. for 1 hour, and the cross-linking index at 250 ° C. of the thermosetting die-bonding film is preferably 13000 or less, preferably 12000 or less. More preferred is 10,000 or less. When the cross-linking index at 250 ° C. of the thermosetting die-bonding film after thermosetting is in the above range, it is possible to suppress a decrease in elasticity at a high temperature of the thermosetting die-bonding film, and to improve heat reflow resistance. Can do. On the other hand, the cross-linking index at 250 ° C. of the thermosetting die-bonding film after thermosetting is preferably 1.5 or more, more preferably 10 or more, from the viewpoint of stress relaxation at high temperatures.

  The elongation at break at 0 ° C. of the thermosetting die-bonding films 3, 3 ′ before thermosetting is preferably 5% or more and 500% or less, more preferably 10% or more and 450% or less. Thereby, the breakability in the low temperature of a thermosetting type die-bonding film can be made favorable.

  The breaking elongation F1 at 0 ° C. of the dicing film 11 and the breaking elongation F2 at 0 ° C. of the thermosetting die-bonding films 3 and 3 ′ before thermosetting satisfy the relationship of F1> F2. preferable. Thereby, it is possible to prevent the thermosetting die-bonding film from excessively following the expansion of the dicing film during the expansion, and the thermosetting die-bonding film can be favorably broken.

  It is preferable that the cross-linking index E1 at 0 ° C. of the dicing film 11 and the cross-linking index E2 at 0 ° C. of the thermosetting die-bonding films 3 and 3 ′ before thermosetting satisfy the relationship of E1> E2. Thereby, the elasticity of the thermosetting die-bonding film at a low temperature can be made higher than the elasticity of the dicing film. In other words, the flexibility or viscosity of the thermosetting die-bonding film at a low temperature can be reduced. The state can be made lower than the viscosity, and the breakability of the thermosetting die-bonding film at a low temperature can be further improved.

  In the thermosetting die-bonding films 3 and 3 ′ before thermosetting, the glass transition temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. By setting the glass transition temperature within the above range, the crystallinity of the thermosetting die-bonding film or the degree of aggregation of the molecular chains can be increased, and the breakability when expanded at low temperatures can be improved. Although the upper limit of the glass transition temperature is not particularly limited, it is preferably 60 ° C. or less, and more preferably 50 ° C. or less, from the viewpoint of wafer lamination of the thermosetting die bond film.

  The layer structure of the thermosetting die-bonding film is not particularly limited. For example, the thermosetting die-bonding film is composed of only a single adhesive layer such as thermosetting die-bonding films 3, 3 ′ (see FIGS. 1 and 2) or a single-layer film. The thing which laminated | stacked the adhesive bond layer, the thing of the multilayered structure which formed the adhesive bond layer in the single side | surface or both surfaces of a core material, etc. are mentioned. Examples of the core material include a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, and a polycarbonate film), a resin substrate reinforced with glass fibers or plastic non-woven fibers, a silicon substrate, a glass substrate, or the like. Is mentioned. When the thermosetting die-bonding film has a multilayer structure, each characteristic may be within a predetermined numerical range as the entire thermosetting die-bonding film having a multilayer structure.

  A preferable example of the adhesive composition constituting the thermosetting die-bonding films 3 and 3 ′ is a combination of a thermoplastic resin and a thermosetting resin.

  Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more. In particular, an epoxy resin containing a small amount of ionic impurities or the like that corrode semiconductor elements is preferable. Moreover, as a hardening | curing agent of an epoxy resin, a phenol resin is preferable.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. Biphenyl type, naphthalene type, fluorene type, phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or hydantoin type, trisglycidyl isocyanurate Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. Of these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like.

  Further, the phenol resin acts as a curing agent for the epoxy resin, for example, a novolac type phenol resin such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a tert-butylphenol novolac resin, a nonylphenol novolac resin, Examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

  The thermosetting resin is preferably a solid thermosetting resin at 23 ° C. Thereby, the softness | flexibility of the thermosetting die-bonding film under low temperature can be suppressed, and breakability can be improved. Commercially available products can be suitably used as the thermosetting resin that is solid at 23 ° C. For example, AER-8039 (Asahi Kasei Epoxy, melting point 78 ° C), BREN-105 (Nippon Kayaku, Melting point 64 ° C), BREN-S (manufactured by Nippon Kayaku, melting point 83 ° C), CER-3000L (manufactured by Nippon Kayaku, melting point 90 ° C), EHPE-3150 (manufactured by Daicel Chemical, melting point 80 ° C), EPPN-501HY ( Nippon Kayaku, melting point 60 ° C), ESN-165M (manufactured by Nippon Steel Chemical, melting point 76 ° C), ESN-175L (manufactured by Nippon Steel Chemical, melting point 90 ° C), ESN-175S (manufactured by Nippon Steel Chemical, melting point 67 ° C), ESN -355 (manufactured by Nippon Steel Chemical Co., melting point 55 ° C), ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., melting point 75 ° C), ESPD-295 (manufactured by Sumitomo Chemical Co., Ltd., melting point 69 ° C), EXA-7335 Dainippon Ink, melting point 99 ° C), EXA-7337 (Dainippon Ink, melting point 70 ° C), HP-7200H (Dainippon Ink, melting point 82 ° C), TEPIC-SS (Nissan Chemical, melting point 108 ° C) , KI-3000 (manufactured by Toto Kasei, melting point 64 ° C.), YDC-1312 (manufactured by Toto Kasei, melting point 141 ° C.), YDC-1500 (manufactured by Toto Kasei, melting point 101 ° C.), YL-6121HN (manufactured by JER, melting point 130 ° C.) ), YSLV-120TE (manufactured by Toto Kasei, melting point 113 ° C.), YSLV-80XY (manufactured by Toto Kasei, melting point 80 ° C.), YX-4000H (manufactured by JER, melting point 105 ° C.), YX-4000K (manufactured by JER, melting point 107 ° C.) ), ZX-650 (manufactured by Toto Kasei, melting point 85 ° C.), Epicoat 1001 (manufactured by JER, melting point 64 ° C.), Epicoat 1002 (manufactured by JER, melting point 78 ° C.), Pikoto 1003 (JER Co., Ltd., melting point 89 ° C.), Epikote 1004 (JER Co., Ltd., melting point 97 ° C.), Epikote 1006FS (JER Co., Ltd., melting point 112 ° C.) can be mentioned.

  Moreover, as a phenol resin, DL-65 (Maywa Kasei, melting point 65 degreeC), DL-92 (Maywa Kasei, melting point 92 degreeC), DPP-L (Nippon Petroleum, melting point 100 degreeC), GS-180 ( Manufactured by Gunei Chemical Co., Ltd., melting point 83 ° C), GS-200 (manufactured by Gunei Chemical Co., melting point 100 ° C), H-1 (manufactured by Meiwa Kasei Co., Ltd., melting point 79 ° C), H-4 (manufactured by Meiwa Kasei Co., Ltd., melting point 71 ° C), HE-100C-15 (manufactured by Sumitomo Chemical, melting point 73 ° C), HE-510-05 (manufactured by Sumitomo Chemical, melting point 75 ° C), HF-1 (manufactured by Meiwa Kasei, melting point 84 ° C), HF-3 (manufactured by Meiwa Kasei) , Melting point 96 ° C), MEH-7500 (Maywa Kasei, melting point 111 ° C), MEH-7500-3S (Maywa Kasei, melting point 83 ° C), MEH-7800H (Maywa Kasei, melting point 86.5 ° C), MEH -7800-3L (Maywa Kasei, melting point 72 ° C), EH-7851 (Maywa Kasei, melting point 78 ° C), MEH-7851-3H (Maywa Kasei, melting point 105 ° C), MEH-7851-4H (Maywa Kasei, melting point 130 ° C), MEH-7851SS (Maywa Kasei) , Melting point 66.5 ° C.), MEH-7851S (Maywa Kasei, melting point 73 ° C.), P-1000 (Arakawa Chemical, melting point 63 ° C.), P-180 (Arakawa Chemical, melting point 83 ° C.), P-200 (Arakawa Chemical, melting point 100 ° C), VR-8210 (Mitsui Chemicals, melting point 60 ° C), XLC-3L (Mitsui Chemicals, melting point 70 ° C), XLC-4L (Mitsui Chemicals, melting point 62 ° C), XLC -LL (Mitsui Chemicals, melting point 75 degreeC) etc. can be mentioned.

  The mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of the epoxy group in the epoxy resin component. . More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.

  Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.

  The acrylic resin is not particularly limited, and includes one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples thereof include a polymer (acrylic copolymer) as a component. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include an ethylhexyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a stearyl group, an octadecyl group, and a dodecyl group.

  Among the acrylic resins, an acrylic copolymer is particularly preferable for the reason of improving cohesion. Examples of the acrylic copolymer include a copolymer of ethyl acrylate and methyl methacrylate, a copolymer of acrylic acid and acrylonitrile, and a copolymer of butyl acrylate and acrylonitrile.

  The glass transition temperature (Tg) of the acrylic resin is preferably −30 ° C. or higher and 30 ° C. or lower, and more preferably −20 or higher and 15 ° C. When the glass transition temperature of the acrylic resin is −30 ° C. or higher, the thermosetting die bond film is hardened and breakability is improved, and when it is 30 ° C. or lower, the wafer laminating property at low temperature is improved. Examples of the acrylic resin having a glass transition temperature of −30 ° C. or higher and 30 ° C. or lower include Nagase ChemteX Corporation: SG-708-6 (glass transition temperature: 4 ° C.), SG-790 (glass transition temperature: − 25 ° C.), WS-023 (glass transition temperature: −5 ° C.), SG-70L (glass transition temperature: −13 ° C.), SG-80H (glass transition temperature: 7.5 ° C.), SG-P3 (glass transition) Temperature: 12 ° C.).

  In addition, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Carboxyl group-containing monomers such as acid anhydride monomers such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyla Hydroxyl group-containing monomers such as relate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate.

  The blending ratio of the thermosetting resin is not particularly limited as long as the thermosetting die-bonding films 3 and 3 ′ exhibit a function as a thermosetting type when heated under a predetermined condition. It is preferably in the range of wt%, more preferably in the range of 10 to 50 wt%.

  Among the thermosetting die-bonding films 3 and 3 ′, an epoxy resin, a phenol resin, and an acrylic resin are contained, the total weight of the epoxy resin and the phenol resin is X, and the weight of the acrylic resin is Y X / (X + Y) is preferably 0.3 or more and less than 0.9, more preferably 0.35 or more and less than 0.85, and 0.4 or more and less than 0.8. Is more preferable. While the epoxy resin and the phenol resin are easily broken as the content increases, the adhesion to the semiconductor wafer 4 decreases. In addition, as the content of the acrylic resin increases, the thermosetting die-bonding films 3 and 3 ′ are less likely to be broken during bonding and handling, and the workability is improved, while being less likely to be broken. Therefore, by setting X / (X + Y) to 0.3 or more, when the semiconductor element 5 is obtained from the semiconductor wafer 4 by stealth dicing, the thermosetting die-bonding films 3, 3 ′ and the semiconductor wafer 4 are simultaneously broken. It becomes easier. Moreover, workability | operativity can be made favorable by making X / (X + Y) less than 0.9.

  When the thermosetting die-bonding films 3 and 3 ′ of the present invention are previously crosslinked to some extent, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer is added as a crosslinking agent during production. I can keep it. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.

  A conventionally well-known thing can be employ | adopted as said crosslinking agent. In particular, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. When the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, which is not preferable. On the other hand, if it is less than 0.05 parts by weight, the cohesive force is insufficient, which is not preferable. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.

  Further, a filler can be appropriately blended in the thermosetting die-bonding films 3 and 3 ′ depending on the application. The blending of the filler enables imparting conductivity, improving thermal conductivity, adjusting the elastic modulus, and the like. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferable from the viewpoints of characteristics such as improvement in handleability, improvement in thermal conductivity, adjustment of melt viscosity, and imparting thixotropic properties. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate whisker. , Boron nitride, crystalline silica, amorphous silica and the like. These can be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable. Further, from the viewpoint that the above properties are well balanced, crystalline silica or amorphous silica is preferable. In addition, a conductive substance (conductive filler) may be used as the inorganic filler for the purpose of imparting conductivity and improving thermal conductivity. Examples of the conductive filler include metal powder in which silver, aluminum, gold, cylinder, nickel, conductive alloy and the like are made into a spherical shape, needle shape and flake shape, metal oxide such as alumina, amorphous carbon black, graphite and the like.

  The average particle size of the filler is preferably 0.005 to 10 μm, and more preferably 0.005 to 1 μm. This is because when the average particle size of the filler is 0.005 μm or more, the wettability to the adherend and the adhesiveness can be improved. Moreover, by setting it as 10 micrometers or less, while being able to make the effect of the filler added for provision of said each characteristic sufficient, heat resistance can be ensured. In addition, the average particle diameter of a filler is the value calculated | required, for example with the photometric type particle size distribution analyzer (The product made from HORIBA, apparatus name; LA-910).

  The content when the thermosetting die bond film contains an inorganic filler is preferably 10% by weight or more and 90% by weight or less with respect to the total amount of the adhesive composition for forming the thermosetting die bond film, It is more preferably 20% by weight or more and 70% by weight or less, and further preferably 30% by weight or more and 60% by weight or less. By setting it as the above upper limit or less, it is possible to prevent the tensile storage elastic modulus from being increased, and it is possible to improve the wettability and adhesion to the adherend. Moreover, by setting it as the said minimum or more, a thermosetting die-bonding film can be suitably fractured | ruptured with a tensile stress.

  In addition to the filler, other additives can be appropriately blended in the thermosetting die bond films 3 and 3 ′ as necessary. Examples of other additives include flame retardants, silane coupling agents, ion trapping agents, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like. These can be used alone or in combination of two or more. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like. These compounds can be used alone or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and bismuth hydroxide. These can be used alone or in combination of two or more.

  A thermosetting catalyst may be used as a constituent material of the thermosetting die bond film. As the content, when the thermosetting die-bonding film contains an acrylic resin, an epoxy resin, and a phenol resin, 0.01 to 5 parts by weight is preferable with respect to 100 parts by weight of the acrylic resin component, and 0.1 to 3 parts by weight is preferable. More preferred. By setting the content to be equal to or more than the above lower limit, epoxy groups that have not been reacted at the time of die bonding can be polymerized in a subsequent step, and the unreacted epoxy groups can be reduced or eliminated. As a result, the semiconductor element can be bonded and fixed on the adherend to manufacture a semiconductor device without peeling. On the other hand, by making the blending ratio not more than the above upper limit, it is possible to prevent the occurrence of curing inhibition.

  The thermosetting catalyst is not particularly limited, and examples thereof include imidazole compounds, triphenylphosphine compounds, amine compounds, triphenylborane compounds, and trihalogenborane compounds. These can be used alone or in combination of two or more.

  Examples of the imidazole compound include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11Z), 2-heptadecylimidazole (trade name; C17Z), and 1,2-dimethylimidazole (product). Name: 1.2 DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1- Benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2 -Undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl 2-phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; 2MZ-A) ), 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; C11Z-A), 2,4-diamino-6- [2'- Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl -S-triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydride Carboxymethyl-methylimidazole (trade name; 2P4MHZ-PW), and the like (all made by Shikoku Kasei Co., Ltd.).

  The triphenylphosphine compound is not particularly limited, and examples thereof include triorganophosphines such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and diphenyltolylphosphine. Fin, tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC), methoxymethyltriphenylphosphonium (trade name) ; TPP-MOC), benzyltriphenylphosphonium chloride (trade name; TPP-ZC) and the like (all manufactured by Hokuko Chemical Co., Ltd.). The triphenylphosphine compound is preferably substantially insoluble in the epoxy resin. It can suppress that thermosetting progresses too much that it is insoluble with respect to an epoxy resin. Examples of the thermosetting catalyst having a triphenylphosphine structure and substantially insoluble in the epoxy resin include methyltriphenylphosphonium (trade name: TPP-MB). The “insoluble” means that the thermosetting catalyst composed of a triphenylphosphine compound is insoluble in a solvent composed of an epoxy resin, and more specifically, a temperature range of 10 to 40 ° C. It means that 10% by weight or more does not dissolve.

  The triphenylborane compound is not particularly limited, and examples thereof include tri (p-methylphenyl) phosphine. The triphenylborane compound further includes those having a triphenylphosphine structure. The compound having the triphenylphosphine structure and the triphenylborane structure is not particularly limited. For example, tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; (TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S), and the like (all manufactured by Hokuko Chemical Co., Ltd.).

  The amino compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella Chemifa Corporation), dicyandiamide (manufactured by Nacalai Tesque Corporation), and the like.

  The trihalogen borane compound is not particularly limited, and examples thereof include trichloroborane.

  The thickness of the thermosetting die-bonding films 3, 3 ′ (total thickness in the case of a laminate) is not particularly limited, but can be selected, for example, from the range of 1 to 200 μm, preferably 5 to 100 μm, more preferably Is 10-80 μm.

  The thermosetting die bond films 3, 3 'of the dicing die bond films 10, 12 are preferably protected by a separator (not shown). The separator has a function as a protective material for protecting the thermosetting die-bonding films 3 and 3 ′ until practical use. Further, the separator can be used as a support substrate when transferring the thermosetting die-bonding films 3 and 3 ′ to the pressure-sensitive adhesive layer 2. The separator is peeled off when a workpiece is stuck on the thermosetting die-bonding films 3, 3 'of the dicing die-bonding film. As the separator, a plastic film or paper surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, a fluorine release agent, or a long-chain alkyl acrylate release agent can be used.

<Manufacturing method of dicing die bond film>
The dicing die bond films 10 and 12 according to the present embodiment are produced as follows, for example.
First, the base material 1 can be formed by a conventionally known film forming method. Examples of the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.

  Next, after a pressure-sensitive adhesive composition solution is applied onto the substrate 1 to form a coating film, the coating film is dried under predetermined conditions (heat-crosslinked as necessary), and the pressure-sensitive adhesive layer 2 is formed. Form. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 80 to 150 ° C. and the drying time is 0.5 to 5 minutes. Moreover, after apply | coating an adhesive composition on a separator and forming a coating film, the coating film may be dried on the said drying conditions, and the adhesive layer 2 may be formed. Then, the adhesive layer 2 is bonded together with the separator on the base material 1. Thereby, the dicing film 11 is produced. At this time, the surface of the dicing film bonded to the thermosetting die bond film may be irradiated with ultraviolet rays in advance.

The thermosetting die-bonding films 3, 3 ′ are produced, for example, as follows.
First, an adhesive composition solution that is a material for forming the thermosetting die-bonding films 3 and 3 ′ is prepared. As described above, the adhesive composition solution contains the adhesive composition, filler, and other various additives.

  Next, the adhesive composition solution is applied onto the base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form an adhesive layer. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 70 to 160 ° C. and the drying time is 1 to 5 minutes. Moreover, after apply | coating an adhesive composition solution on a separator and forming a coating film, you may dry an application film on the said drying conditions, and may form an adhesive bond layer. Then, an adhesive bond layer is bonded together with a separator on a base material separator.

  Subsequently, the separator is peeled off from each of the dicing film 11 and the adhesive layer, and the adhesive layer and the pressure-sensitive adhesive layer are bonded to each other so as to be a bonding surface. Bonding can be performed by, for example, pressure bonding. At this time, the lamination temperature is not particularly limited, and for example, 30 to 70 ° C is preferable, and 40 to 60 ° C is more preferable. Moreover, a linear pressure is not specifically limited, For example, 0.1-20 kgf / cm is preferable and 1-10 kgf / cm is more preferable. Next, the base material separator on the adhesive layer is peeled off, and the dicing die-bonding film according to the present embodiment is obtained.

(Method for manufacturing semiconductor device)
Next, a method for manufacturing a semiconductor device using the dicing die bond film 12 will be described. 3 to 6 are schematic cross-sectional views for explaining one method of manufacturing the semiconductor device according to this embodiment. First, the modified region is formed on the division line 4L by irradiating the division line 4L of the semiconductor wafer 4 with laser light. This method is a method of aligning a condensing point inside a semiconductor wafer, irradiating a laser beam along a grid-like division planned line, and forming a modified region inside the semiconductor wafer by ablation by multiphoton absorption. . What is necessary is just to adjust suitably within the range of the following conditions as laser beam irradiation conditions.

<Laser irradiation conditions>
(A) Laser light
Laser light source Semiconductor laser pumped Nd: YAG laser
Wavelength 1064nm
Laser light spot cross-sectional area 3.14 × 10 ⁻⁸ cm ²
Oscillation form Q switch pulse
Repeat frequency 100 kHz or less
Pulse width 1μs or less
Output 1mJ or less
Laser light quality TEM00
Polarization characteristics Linearly polarized (B) condensing lens
Magnification 100 times or less
NA 0.55
Transmittance with respect to laser light wavelength: 100% or less (C) Moving speed of the table on which the semiconductor substrate is placed 280 mm / second or less

  In addition, since the method of irradiating a laser beam to form a modified region on the planned division line 4L is described in detail in Japanese Patent No. 3408805 and Japanese Patent Application Laid-Open No. 2003-338567, details here. Detailed explanation will be omitted.

  Next, as shown in FIG. 4, the semiconductor wafer 4 after the formation of the modified region is pressure-bonded onto the thermosetting die-bonding film 3 ', and this is bonded and held (fixing step). This step is performed while pressing with a pressing means such as a pressure roll. The attaching temperature at the time of mounting is not particularly limited, but is preferably in the range of 40 to 80 ° C. This is because warping of the semiconductor wafer 4 can be effectively prevented and the influence of expansion and contraction of the dicing die-bonding film can be reduced.

  Next, by applying a tensile stress to the dicing die bond film 12, the semiconductor wafer 4 and the thermosetting die bond film 3 'are broken at the division line 4L to form the semiconductor chip 5 (chip forming step). In this step, for example, a commercially available wafer expansion device can be used. Specifically, as shown in FIG. 5A, a dicing ring 31 is attached to the periphery of the pressure-sensitive adhesive layer 2 of the dicing die-bonding film 12 to which the semiconductor wafer 4 is bonded, and then the wafer expansion device 32 is attached. Fix it. Next, as shown in FIG. 5B, the push-up portion 33 is raised to apply tension to the dicing die-bonding film 12.

  This chip forming step is preferably performed under conditions of −30 ° C. to 20 ° C., preferably performed under conditions of −25 to 15 ° C., and performed under conditions of −15 to 5 ° C. More preferably. By executing the chip forming step under the above temperature conditions, the crystallinity of the thermosetting die-bonding film 3 ′ can be increased and good breakability can be obtained.

  In the chip formation step, the expanding speed (speed at which the push-up part rises) is preferably 100 to 400 mm / second, more preferably 100 to 350 mm / second, and further preferably 100 to 300 mm / second. By setting the expanding speed to 100 mm / second or more, the semiconductor wafer 4 and the thermosetting die-bonding film 3 ′ can be easily broken almost simultaneously. Moreover, it can prevent that the dicing film 11 fractures | ruptures by setting an expanding speed to 400 mm / second or less.

  In the chip formation step, the amount of expand is preferably 6 to 12%. The amount of expansion may be adjusted as appropriate according to the chip size to be formed within the numerical range. In addition, in this specification, the amount of expand is the value (%) of the surface area which increased by the expansion with the surface area of the dicing film before expansion as 100%. By making the expand amount 6% or more, the semiconductor wafer 4 and the thermosetting die bond film 3 can be easily broken. Moreover, it can prevent that the dicing film 11 fractures | ruptures by making expand amount into 12% or less.

  Thus, by applying a tensile stress to the dicing die bond film 12, cracks are generated in the thickness direction of the semiconductor wafer 4 starting from the modified region of the semiconductor wafer 4, and the thermosetting type is in close contact with the semiconductor wafer 4. The die bond film 3 ′ can be broken, and the semiconductor chip 5 with the thermosetting die bond film 3 ′ can be obtained.

  Next, in order to peel off the semiconductor chip 5 adhered and fixed to the dicing die bond film 12, the semiconductor chip 5 is picked up (pickup process). The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, a method of pushing up the individual semiconductor chips 5 from the dicing die bond film 12 side with a needle and picking up the pushed-up semiconductor chips 5 with a pickup device may be mentioned.

  Here, since the pressure-sensitive adhesive layer 2 is an ultraviolet curable type, the pickup is performed after the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays. Thereby, the adhesive force of the pressure-sensitive adhesive layer 2 to the thermosetting die-bonding film 3 ′ is reduced, and the semiconductor chip 5 can be easily peeled off. As a result, the pickup can be performed without damaging the semiconductor chip 5. Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary. In addition, when the dicing die-bonding film by which the thermosetting die-bonding film was bonded to the dicing film hardened | cured with ultraviolet rays is used, the ultraviolet irradiation here is unnecessary.

  Next, as shown in FIG. 6, the picked-up semiconductor chip 5 is die-bonded to the adherend 6 via a thermosetting die-bonding film 3 '(temporary fixing step). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, and a separately manufactured semiconductor chip. The adherend 6 may be, for example, a deformable adherend that can be easily deformed or a non-deformable adherend (such as a semiconductor wafer) that is difficult to deform.

  A conventionally well-known thing can be used as said board | substrate. As the lead frame, a metal lead frame such as a Cu lead frame or a 42 Alloy lead frame, or an organic substrate made of glass epoxy, BT (bismaleimide-triazine), polyimide, or the like can be used. However, the present invention is not limited to this, and includes a circuit board that can be used by bonding and fixing a semiconductor element and electrically connecting the semiconductor element.

  The shear adhesive strength at 25 ° C. at the time of temporary fixing of the thermosetting die bond film 3 ′ is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa with respect to the adherend 6. When the shear adhesive strength of the thermosetting die bond film 3 is at least 0.2 MPa or more, during the wire bonding process, the thermosetting die bond film 3 and the semiconductor chip 5 or the There is little occurrence of shear deformation on the adhesive surface with the adherend 6. That is, the semiconductor element is less likely to move due to ultrasonic vibration during wire bonding, thereby preventing the success rate of wire bonding from decreasing. Further, the shear adhesive strength at 175 ° C. at the time of temporarily fixing the thermosetting die bond film 3 ′ is preferably 0.01 MPa or more, more preferably 0.01 to 5 MPa with respect to the adherend 6. .

  Next, wire bonding is performed in which the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor chip 5 are electrically connected by the bonding wire 7 (wire bonding step). As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire or the like is used. The temperature at the time of wire bonding is 80 to 250 ° C, preferably 80 to 220 ° C. The heating time is several seconds to several minutes. The connection is performed by a combination of vibration energy by ultrasonic waves and crimping energy by applying pressure while being heated so as to be within the temperature range. This step can be performed without thermosetting the thermosetting die-bonding film 3a. Further, the semiconductor chip 5 and the adherend 6 are not fixed by the thermosetting die bond film 3a in the process of this step.

  Next, the semiconductor chip 5 is sealed with the sealing resin 8 (sealing step). This step is performed to protect the semiconductor chip 5 and the bonding wire 7 mounted on the adherend 6. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. Although the heating temperature at the time of resin sealing is normally performed at 175 degreeC for 60 to 90 second, this invention is not limited to this, For example, it can cure at 165 to 185 degreeC for several minutes. Thereby, the sealing resin is cured, and the semiconductor chip 5 and the adherend 6 are fixed through the thermosetting die bond film 3. That is, in the present invention, even when the post-curing step described later is not performed, the thermosetting die-bonding film 3 can be fixed in this step, and the number of manufacturing steps can be reduced and the semiconductor device can be reduced. This can contribute to shortening the manufacturing period.

  In the post-curing step, the sealing resin 8 that is insufficiently cured in the sealing step is completely cured. Even if the thermosetting die-bonding film 3a is not completely cured in the sealing process, the thermosetting die-bonding film 3a can be completely cured together with the sealing resin 8 in this process. Although the heating temperature in this process changes with kinds of sealing resin, it exists in the range of 165-185 degreeC, for example, and heating time is about 0.5 to 8 hours.

  In the embodiment described above, after the semiconductor chip 5 with the thermosetting die bond film 3 ′ is temporarily fixed to the adherend 6, the wire bonding step is performed without completely thermosetting the thermosetting die bond film 3 ′. explained. However, in the present invention, after the semiconductor chip 5 with the thermosetting die bond film 3 ′ is temporarily fixed to the adherend 6, the thermosetting die bond film 3 ′ is thermoset, and then the wire bonding process is performed. A normal die bonding process may be performed. In this case, the thermosetting die-bonding film 3 ′ after thermosetting preferably has a shear adhesive strength of 0.01 MPa or more at 175 ° C., more preferably 0.01 to 5 MPa. By setting the shear adhesive strength at 175 ° C. after thermosetting to 0.01 MPa or more, the thermosetting die-bonding film 3 ′ and the semiconductor chip 5 or the deposition are caused by ultrasonic vibration or heating in the wire bonding process. This is because shear deformation can be prevented from occurring on the bonding surface with the body 6.

  In addition, the dicing die-bonding film of this invention can be used suitably also when laminating | stacking a several semiconductor chip and carrying out three-dimensional mounting. At this time, the thermosetting die bond film and the spacer may be laminated between the semiconductor chips, or only the thermosetting die bond film may be laminated between the semiconductor chips without laminating the spacers. It can be appropriately changed according to the above.

<< Second Embodiment >>
In the first embodiment, the semiconductor wafer 4 on which the modified region is formed in advance is pressure-bonded onto the thermosetting die bond film 3 ′. In the second embodiment, a semiconductor wafer is pressure-bonded to the thermosetting die bond film 3 ′, and then a laser beam is irradiated to the semiconductor wafer disposed on the thermosetting die bond film 3 ′ to form a modified region inside. To do. The conditions of the first embodiment can be suitably employed for the pressure bonding conditions and the laser light irradiation conditions.

<< Third Embodiment >>
Next, a method for manufacturing a semiconductor device that employs a process of forming grooves on the surface of a semiconductor wafer and then performing backside grinding will be described below.

  7 and 8 are schematic cross-sectional views for explaining another method for manufacturing the semiconductor device according to the present embodiment. First, as shown in FIG. 7A, a groove 4 </ b> S that does not reach the back surface 4 </ b> R is formed on the front surface 4 </ b> F of the semiconductor wafer 4 by the rotating blade 41. When forming the grooves 4S, the semiconductor wafer 4 is supported by a support base (not shown). The depth of the groove 4S can be appropriately set according to the thickness of the semiconductor wafer 4 and the expanding conditions. Next, as shown in FIG. 7B, the semiconductor wafer 4 is supported on the protective base material 42 so that the surface 4F comes into contact therewith. Thereafter, back grinding is performed with the grinding wheel 45 to expose the groove 4S from the back surface 4R. In addition, a conventionally well-known sticking apparatus can be used for affixing the protective base material 42 to a semiconductor wafer, and a conventionally well-known grinding apparatus can also be used for back surface grinding.

  Next, as shown in FIG. 8, the semiconductor wafer 4 with the grooves 4 </ b> S exposed is pressure-bonded onto the dicing die-bonding film 12, and this is adhered and held and fixed (temporary fixing step). Thereafter, the protective substrate 42 is peeled off, and tension is applied to the dicing die-bonding film 12 by the wafer expansion device 32. Thereby, the thermosetting die-bonding film 3 ′ is broken to form the semiconductor chip 5 (chip forming process). Note that the temperature, the expansion speed, and the amount of expansion in the chip formation step are the same as those in the case where the modified region is formed on the division planned line 4L by irradiating the laser beam. Since the subsequent steps are the same as the case where the modified region is formed on the planned division line 4L by irradiating the laser beam, the description here will be omitted.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in this example are not intended to limit the gist of the present invention only to those unless otherwise limited.

<Example 1>
(Production of dicing film)
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirring device, 100 parts of 2-ethylhexyl acrylate (hereinafter referred to as “2EHA”), 2-hydroxyethyl acrylate (hereinafter referred to as “HEA”) .) 13 parts, 0.3 part of benzoyl peroxide and 80 parts of toluene were added and polymerized in a nitrogen stream at 60 ° C. for 8 hours to obtain an acrylic polymer A. To this acrylic polymer A, 1 part of 2-methacryloyloxyethyl isocyanate (hereinafter referred to as “MOI”) is added and subjected to an addition reaction in an air stream at 50 ° C. for 50 hours to obtain an acrylic polymer A ′. It was.

  Next, for 100 parts of acrylic polymer A ′, 2 parts of a polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and a photopolymerization initiator (trade name “Irgacure 184”, Ciba Special) 3 parts) (manufactured by T Chemicals) was added to prepare an adhesive solution (sometimes referred to as “adhesive solution A”).

  The pressure-sensitive adhesive solution A prepared above was applied onto the silicone-treated surface of the PET release liner and dried by heating at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. Next, the HL film (70 μm thickness) manufactured by Ron Seal Industry Co., Ltd. was bonded to the pressure-sensitive adhesive layer surface, and stored at 23 ° C. for 72 hours to obtain a dicing film.

(Production of thermosetting die bond film)
Acrylic resin (trade name “SG-708-6” manufactured by Nagase ChemteX Corporation): 100 parts, epoxy resin (trade name “JER1010” manufactured by Mitsubishi Chemical Corporation): 204 parts, epoxy resin (trade name “JER828”) Mitsubishi Chemical Co., Ltd.): 224 parts, phenol resin (trade name “MEH-7851ss” manufactured by Meiwa Kasei Co., Ltd.) 320 parts, spherical silica (trade name “SO-25R” manufactured by Admatechs Co., Ltd.): 1050 parts, catalyst (product) 5 parts of the name “2PHZ” (manufactured by Shikoku Kasei) were dissolved in methyl ethyl ketone to prepare an adhesive composition solution having a solid content of 20% by weight.

  The adhesive composition solution was applied as a release liner (separator) on a release film made of a polyethylene terephthalate film having a thickness of 50 μm and then dried at 130 ° C. for 2 minutes to obtain a thickness. A thermosetting die-bonding film having an average thickness of 10 μm was produced.

(Production of dicing die bond film)
The thermosetting die-bonding film was bonded onto the adhesive layer of the dicing film using a hand roller to produce a dicing die-bonding film.

<Example 2>
(Production of dicing film)
The pressure-sensitive adhesive solution A prepared in Example 1 was coated on the surface of the PET release liner that had been subjected to the silicone treatment, and dried by heating at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. Next, it was bonded to the surface of the pressure-sensitive adhesive layer with Funclair NRB # 115 (115 μm thickness) manufactured by Gunze, and stored at 23 ° C. for 72 hours to obtain a dicing film.

(Production of thermosetting die bond film)
Acrylic resin (trade name “SG-708-6” manufactured by Nagase ChemteX Corporation): 100 parts, epoxy resin (trade name “JER1010” manufactured by Mitsubishi Chemical Corporation): 5 parts, phenol resin (trade name “MEH- 7851 ss "manufactured by Meiwa Kasei Co., Ltd .: 6 parts, spherical silica (trade name" SO-25R "manufactured by Admatechs Co., Ltd.): 20 parts dissolved in methyl ethyl ketone, the adhesive composition having a solid content concentration of 20% by weight A solution was prepared.

  The adhesive composition solution was applied as a release liner (separator) on a release-treated film made of a polyethylene terephthalate film having a thickness of 50 μm, and then dried at 130 ° C. for 2 minutes. A thermosetting die-bonding film having a thickness (average thickness) of 10 μm was produced.

(Production of dicing die bond film)
The thermosetting die-bonding film was bonded onto the adhesive layer of the dicing film using a hand roller to produce a dicing die-bonding film.

<Comparative Example 1>
(Dicing film)
The dicing film used in Example 1 was used.

(Production of thermosetting die bond film)
Acrylic resin (trade name “SG-70L” manufactured by Nagase ChemteX Corporation): 100 parts, epoxy resin (trade name “JER1010” manufactured by Mitsubishi Chemical Corporation): 7 parts, phenol resin (trade name “MEH-7800- 4L "manufactured by Meiwa Kasei Co., Ltd.): 7 parts were dissolved in methyl ethyl ketone to prepare an adhesive composition solution having a solid content of 20% by weight.

  The adhesive composition solution was applied as a release liner (separator) on a release film made of a polyethylene terephthalate film having a thickness of 50 μm and then dried at 130 ° C. for 2 minutes to obtain a thickness. A thermosetting die-bonding film having an average thickness of 10 μm was produced.

(Production of dicing die bond film)
The thermosetting die-bonding film A was bonded onto the adhesive layer of the dicing film using a hand roller to prepare a dicing / die-bonding film.

<Comparative example 2>
(Dicing film)
The dicing film used in Example 1 was used.

(Preparation of thermal die bond film)
Acrylic resin (trade name “SG-708-6” manufactured by Nagase ChemteX Corporation): 100 parts, epoxy resin (trade name “JER1010” manufactured by Mitsubishi Chemical Corporation): 204 parts, epoxy resin (trade name “JER828”) Mitsubishi Chemical Co., Ltd.): 324 parts, phenol resin (trade name “MEH-7800-4L”, manufactured by Meiwa Kasei Co., Ltd.) 320 parts, spherical silica (trade name “SO-25R”, manufactured by Admatechs Co., Ltd.): 1500 parts, catalyst 5 parts (trade name “2PHZ” manufactured by Shikoku Chemicals) were dissolved in methyl ethyl ketone to prepare an adhesive composition solution having a solid content of 20% by weight.

  The adhesive composition solution was applied as a release liner (separator) on a release film made of a polyethylene terephthalate film having a thickness of 50 μm and then dried at 130 ° C. for 2 minutes to obtain a thickness. A thermosetting die-bonding film having an average thickness of 10 μm was produced.

(Production of dicing die bond film)
The thermosetting die-bonding film was bonded onto the pressure-sensitive adhesive layer of the dicing tape A using a hand roller to prepare a dicing / die-bonding film.

<Evaluation>
The following evaluation was performed about the dicing die-bonding film produced in the Example and the comparative example. The results are shown in Table 1.

(Measurement of cross-linking index)
The cross-linking index was determined by the following formula.
Cross-linking index (cm ³ / mol) = 3RT / E ′
(In the formula, E ′ is a storage elastic modulus [Pa], R is a gas constant (= 8.31 J / mol · K), and T is an absolute temperature [K].)

  The storage elastic modulus was determined by the following procedure. A thermosetting die-bonding film (laminated to a thickness of 200 μm) and a dicing film were cut into a strip shape with a width of 10 mm and a length of 40 mm, respectively, with a cutter knife, and the solid viscoelasticity measuring device (RSA III, manufactured by Rheometric Scientific) Then, the dynamic storage elastic modulus was measured at a frequency of 1 Hz in a tensile mode at −50 to 300 ° C., a distance between chucks of 22.5 mm, a heating rate of 10 ° C./min. It calculated | required by reading the storage elastic modulus in 0 degreeC in that case.

  About the storage elastic modulus after thermosetting, the thermosetting type die-bonding film was heat-processed for 1 hour with the dryer of 175 degreeC, and it measured like the above after thermosetting processing. It calculated | required by reading the storage elastic modulus in 250 degreeC in that case.

(Measurement of elongation at break)
A thermosetting die-bonding film (laminated to a thickness of 100 μm) and a dicing film are formed into a strip shape with a length of 120 mm and a width of 10 mm, and stretched between the chucks at the time of breaking by stretching under conditions of an initial chuck distance of 20 mm and a tensile speed of 100 mm / min. The distance x (mm) was obtained, and the elongation at break was obtained from the following formula. Autograph AG-IS (manufactured by Shimadzu Corporation) was used as the tensile tester.
Elongation at break (%) = {(x−20) / 20} × 100

(Evaluation of breakability)
Using the ML300-Integration manufactured by Tokyo Seimitsu Co., Ltd. as the laser processing apparatus, align the condensing point inside the semiconductor wafer, and from the circuit forming surface side of the semiconductor wafer along the grid-like (10 mm × 10 mm) division planned line Laser beam was irradiated to form a modified region inside the semiconductor wafer. As the semiconductor wafer, a silicon wafer (thickness: 75 μm, outer diameter: 12 inches) was used. The laser light irradiation conditions were as follows.
(A) Laser light
Laser light source Semiconductor laser pumped Nd: YAG laser
Wavelength 1064nm
Laser light spot cross-sectional area 3.14 × 10 ⁻⁸ cm ²
Oscillation form Q switch pulse
Repetition frequency 100kHz
Pulse width 30ns
Output 20μJ / pulse
Laser light quality TEM00 40
Polarization characteristics Linearly polarized (B) condensing lens
50 times magnification
NA 0.55
60% transmittance for laser wavelength
(C) Moving speed of the table on which the semiconductor substrate is placed 100 mm / second

  After that, a backgrinding protective tape is attached to the semiconductor wafer circuit formation surface, and the back surface (surface opposite to the circuit formation surface) is ground using a DISCO back grinder DGP8760 so that the thickness of the semiconductor wafer is 30 μm. did.

  After the semiconductor wafer and the dicing ring that had been pretreated with the laser beam were bonded to the dicing die bond film, the semiconductor wafer was cleaved and the dicing film was thermally shrunk using a Disco Separator DDS2300.

  That is, first, a dicing die-bonding film was expanded with a cool expander unit under the conditions of an expansion temperature of 0 ° C., an expansion speed of 200 mm / second, and an expansion amount of 12 mm, and the semiconductor wafer and the die-bonding film were cleaved.

Thereafter, the dicing film was thermally contracted with a heat expander unit under the conditions of an expand amount of 10 mm, a heat temperature of 250 ° C., an air volume of 40 L / min, a heat distance of 20 mm, and a rotation speed of 3 ° / sec to obtain an evaluation sample. It was confirmed for all lines using an optical microscope whether the die bond film was cleaved together with the semiconductor chip. It was judged that a line with a portion that could not be broken even partially was impossible, and the breaking rate was calculated based on the following formula.
Breaking rate (%) = (number of broken lines / number of all lines) × 100

(Evaluation of scattering properties of die bond film)
It was confirmed with an optical microscope whether or not the pieces of the die bond film were scattered on the semiconductor chip of the evaluation sample obtained by the procedure for evaluating the breakability.

  In the thermosetting die-bonding films of Examples 1 and 2, the breakability of the chip and the thermosetting die-bonding film at 0 ° C. was good, and no scattering of fragments of the thermosetting die-bonding film was observed. On the other hand, in the thermosetting die-bonding film of Comparative Example 1, although the fragments of the thermosetting die-bonding film were not scattered, the breakability was inferior. This is considered to be due to the fact that the thermosetting die-bonding film has an excessively high crosslinking index at 0 ° C., and the flexibility or viscosity of the thermosetting die-bonding film is increased. Moreover, in the thermosetting die-bonding film of Comparative Example 2, although breakability was good, scattering of fragments of the thermosetting die-bonding film was confirmed. This is thought to be because the cross-linking index at 0 ° C. of the thermosetting die-bonding film is too small, the elasticity or hardness of the thermosetting die-bonding film becomes strong, and the thermosetting die-bonding film breaks at an unintended location. It is done.

  In addition, although the evaluation by a stealth dicing was performed in the present Example, it is thought that the same result is obtained also by the evaluation by a DBG method.

DESCRIPTION OF SYMBOLS 1 Base material 2 Adhesive layer 3, 3 'Thermosetting die-bonding film 4 Semiconductor wafer 5 Semiconductor chip 6 Adhering body 7 Bonding wire 8 Sealing resin 10, 12 Dicing die-bonding film 11 Dicing film

Claims (7)

The thermosetting die bond film is a dicing die bond film laminated on a dicing film in which an adhesive layer is laminated on a substrate,
A dicing die-bonding film in which a cross-linking index at 0 ° C. of the thermosetting die-bonding film before thermosetting is 0.8 or more and 4.0 or less.   2. The dicing die-bonding film according to claim 1, wherein the thermosetting die-bonding film has a cross-linking index of 13000 or less at 250 ° C. after the thermosetting die-bonding film is cured by heating at 175 ° C. for 1 hour.   The dicing die-bonding film according to claim 1 or 2, wherein the elongation at break at 0 ° C of the thermosetting die-bonding film before thermosetting is 5% or more and 500% or less.   The breaking elongation rate F1 at 0 ° C of the dicing film and the breaking elongation rate F2 at 0 ° C of the thermosetting die-bonding film before thermosetting satisfy a relationship of F1> F2. The dicing die-bonding film according to claim 1.   The crosslinking index E1 at 0 ° C. of the dicing film and the crosslinking index E2 at 0 ° C. of the thermosetting die-bonding film before thermosetting satisfy a relationship of E1> E2. The dicing die-bonding film as described in the item. A method for manufacturing a semiconductor device using the dicing die-bonding film according to any one of claims 1 to 5,
Irradiating laser beam to the division line of the semiconductor wafer to form a modified region on the division line; and
Bonding the semiconductor wafer after the modified region formation to the dicing die-bonding film;
By applying a tensile stress to the dicing die bond film at −30 ° C. to 20 ° C., the semiconductor wafer and the thermosetting die bond film constituting the dicing die bond film are broken at the division line. And forming a semiconductor element;
Picking up the semiconductor element together with the thermosetting die-bonding film;
And a step of die-bonding the picked-up semiconductor element to an adherend via the thermosetting die-bonding film. A method for manufacturing a semiconductor device using the dicing die-bonding film according to any one of claims 1 to 5,
Forming a groove on the surface of the semiconductor wafer that does not reach the back surface;
Grinding the back surface of the semiconductor wafer and exposing the groove from the back surface;
Bonding the semiconductor wafer with the groove exposed from the back surface to the dicing die-bonding film;
Under the conditions of −30 ° C. to 20 ° C., by applying a tensile stress to the dicing die bond film, breaking the thermosetting die bond film constituting the dicing die bond film, and forming a semiconductor element;
Picking up the semiconductor element together with the thermosetting die-bonding film;
And a step of die-bonding the picked-up semiconductor element to an adherend via the thermosetting die-bonding film.

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