TW201621994A - Cutting die bond - Google Patents

Abstract

A dicing die bonding sheet comprising a dye-containing adhesive layer on a substrate, wherein the content of the dye in the adhesive layer is 8.3% by mass or less, and L*a between the substrate and the adhesive layer The color difference in the *b* color system is 30~53.

Description

Cutting die bond

The present invention relates to a diced die bond sheet having an adhesive layer on a substrate.

The present application claims priority based on Japanese Patent Application No. 2014-253241, filed on Jan.

A dicing die bond sheet having an adhesive layer on a substrate is used for cutting from a semiconductor wafer and picking up through a semiconductor wafer until the picked semiconductor wafer is attached to a substrate, a lead frame, other semiconductor wafers, and the like. The steps.

In the above-mentioned sheet, the adhesive layer is usually colorless and transparent, so when performing precut processing on the sheet or performing die bonding of the semiconductor wafer, it is difficult to check whether the adhesive layer is next to the semiconductor wafer or semiconductor. The state of the object, such as a wafer. If the adhesive layer does not follow the desired portion, a problem occurs in the manufacturing steps of the semiconductor device. Also, when the adhesive layer is cut by stealth cutting or cold expansion, Since the adhesive layer is colorless and transparent, it is not easy to confirm whether or not the adhesive layer has been reliably cut, resulting in a decrease in the manufacturing efficiency of the semiconductor device.

In the manufacturing step of the semiconductor device, for example, an optical sensor capable of detecting light in a wavelength band of 290 to 450 nm is used to inspect the adhesive layer, but this inspection becomes difficult due to thinning of the adhesive layer.

Among them, as an adhesive layer which is easy to inspect, an adhesive layer containing a pigment which absorbs or reflects light having a wavelength in the range of 290 to 450 nm has been disclosed (see Patent Document 1).

Since such an adhesive layer is colored by containing a pigment, it can be easily visually confirmed whether or not the adhesive layer is present.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-059917

However, the adhesive layer described in Patent Document 1 has a problem in that, in the case where the thickness is small, aggregates or color unevenness may occur, and cracks may occur in the finally obtained semiconductor package, resulting in cracks. Reduced reliability.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a diced die bond sheet which is easy to confirm the presence or absence of an adhesive layer, and to obtain a highly reliable semiconductor package.

In order to solve the above problems, the present invention provides a dicing die bonding sheet comprising a dye-containing adhesive layer on a substrate, wherein the content of the dye in the adhesive layer is 8.3% by mass or less, and the substrate The color difference in the L ^* a ^* b ^* color system with the aforementioned adhesive layer is 30-53.

In the dicing die bond sheet of the present invention, the dye may be a bisazo dye.

In the dicing die bonding sheet of the present invention, the dye may be a dye which does not contain a metal atom or a metal ion in the structure.

According to the present invention, there is provided a dicing die bonding sheet which can easily confirm the presence or absence of an adhesive layer and obtain a highly reliable semiconductor package.

<<Cutting die bonding sheet>>

The dicing die-bonding sheet of the present embodiment is characterized in that the base material is provided with a dye-containing adhesive layer, and the content of the dye in the adhesive layer is 8.3% by mass or less, and the substrate and the adhesive layer are The color difference (hereinafter abbreviated as "ΔE") in the L ^* a ^* b ^* color system is 30 to 53.

In the present specification, the above L ^* , a ^*, and b ^{* are} calculated in accordance with JIS Z 8781-4:2013.

The adhesive layer of the foregoing diced die bond sheet contains a specific amount of dye, and thus the aforementioned chromatic aberration (ΔE) is within a specific range. As a result, it can be easily confirmed whether or not the dicing die bonding sheet has an adhesive layer.

Further, by using the dicing die bonding sheet, when the dicing die bonding sheet is subjected to size cutting, or when the semiconductor wafer is picked up or die-bonded, it is easy to visually confirm whether or not the adhesive layer is followed by the semiconductor. The state of the object to be bonded, such as a wafer or a semiconductor wafer, can be suppressed from occurring in the manufacturing process of a semiconductor device.

Further, by using the above-described dicing die bonding sheet, in the process of manufacturing a semiconductor wafer, it is possible to easily confirm whether or not the adhesive layer is reliably cut even when performing the stealth dicing, thereby suppressing the manufacturing efficiency of the semiconductor device. The reduction is called invisible cutting, which forms a fragile portion inside the wafer by laser irradiation, and cuts the die-bonding piece to which the wafer is attached. The row is expanded to cut the wafer and the aforementioned sheet.

Further, even when the so-called cold expansion is performed, that is, when the adhesive layer which forms the brittle portion at a low temperature is expanded and cut, it is possible to easily visually confirm whether or not the adhesive layer has been reliably cut as in the case of performing the stealth cutting. In this state, it is possible to suppress a decrease in the manufacturing efficiency of the semiconductor device.

Usually, when the above expansion is carried out, it is confirmed whether the adhesive layer has been cut by visual observation or observation by a microscope. However, according to the present invention, it is easy to visually confirm the adhesive layer, and it can be confirmed in a short time. If the adhesive layer is not cut, when the target wafer is picked up, the peripheral wafers are simultaneously lifted, causing problems.

In addition, since the adhesive layer contains a dye and the content of the dye is 8.3% by mass or less, the semiconductor package obtained by cutting the die-bonding sheet described above suppresses cracking of the crack or the joint portion and has high reliability. In the case where the adhesive layer contains a pigment instead of a dye, when the thickness of the adhesive layer is thin, especially when the thickness is about 10 μm or less, cohesive or color unevenness sometimes occurs in the adhesive layer, and finally obtained. Cracks are generated in the semiconductor package, resulting in reduced reliability.

<Substrate>

The color difference (ΔE) between the substrate and the adhesive layer satisfies the aforementioned relationship.

The color of the substrate is not particularly limited as long as it is not the same as the color of the adhesive layer, but is usually preferably white.

The substrate may have an adhesive layer on the surface (hereinafter sometimes referred to simply as "adhesive substrate", and the substrate in contact with the adhesive layer in this case is simply referred to as "support substrate"), or may not have an adhesive layer (hereinafter) The time is simply referred to as "non-adhesive substrate").

When the base material is the above-mentioned adhesive base material, the laminated structure of the support base material and the pressure-sensitive adhesive layer may be integrated, and the relationship between the color difference (ΔE) and the adhesive layer may be satisfied.

The material of the non-adhesive substrate and the support substrate is preferably various resins, and specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) can be exemplified. Etc)), polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, poly Ethyl carbamate, polyurethane acrylate, polyimine, ethylene vinyl acetate copolymer, ionic polymer resin, ethylene/(meth)acrylic acid copolymer, ethylene/(meth) acrylate copolymer Polystyrene, polycarbonate, fluororesin, hydride, modified product, crosslinked product or copolymer of any of these resins.

The non-adhesive substrate and the support substrate may comprise one layer (single layer), or may comprise two or more layers. When multiple layers are included, the materials of the layers may be the same or different, or only a part of the same .

The aforementioned non-adhesive substrate and support base may be appropriately selected according to the purpose. The thickness of the material, but the thickness is preferably 50 to 300 μm, more preferably 60 to 100 μm.

The non-adhesive substrate and the support substrate may be subjected to embossing treatment such as blasting treatment or solvent treatment, or corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, or chromium treatment. Oxidation treatment such as acid treatment, hot air treatment, etc., to improve the adhesion to the layer disposed above it, that is, to the adhesive layer or the adhesive layer. Further, the non-adhesive substrate and the support substrate may be a non-adhesive substrate and a support substrate on which the surface is subjected to a primer treatment.

Among them, in view of suppressing breakage of the substrate due to friction of the blade at the time of cutting, it is preferable that the non-adhesive substrate and the support substrate are subjected to electron beam irradiation treatment on the surface.

[Adhesive layer]

A well-known adhesive layer can be used suitably for the said adhesive layer. When the adhesive layer is colorless, the adhesive substrate reflects the color of the support substrate, and when the adhesive layer is colored (colored), the adhesive substrate reflects the color of the adhesive layer or the support substrate and the adhesive layer. The color of both sides.

The adhesive layer can be formed using an adhesive composition containing various constituent components of the adhesive layer. The content ratio of the nonvolatile components to each other in the adhesive composition is also the same in the adhesive layer.

When the adhesive layer contains a component that is polymerized by irradiation with an energy ray, The semiconductor wafer is picked up by illuminating the energy line to reduce its adhesion. For example, such an adhesive layer can be formed using various adhesive compositions containing an energy ray polymerizable acrylic polymer which is polymerized by energy ray irradiation.

The adhesive composition containing the acrylic polymer and the energy ray-polymerizable compound (adhesive composition (i)), and the polymerization of acrylic acid having a hydroxyl group and having a polymerizable group in a branched chain can be exemplified. An adhesive composition (adhesive composition (ii)) having an amino acid (for example, an acrylic polymer having a hydroxyl group and having a polymerizable group in a branched chain bonded via urethane) and an isocyanate crosslinking agent is more preferably Further containing a solvent.

The above-mentioned adhesive composition may further contain, in addition to the above components, a photopolymerization initiator, or any of various additives such as a dye, a pigment, an anti-deterioration agent, an antistatic agent, a flame retardant, a polyoxymethylene compound, and a chain transfer agent. One.

The thickness of the adhesive layer can be appropriately selected depending on the purpose, but the thickness is preferably from 1 to 100 μm, more preferably from 1 to 60 μm, still more preferably from 1 to 30 μm.

The adhesive composition is obtained, for example, by blending various constituent components of an adhesive layer such as an acrylic polymer.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

The method of mixing the components at the time of mixing is not particularly limited, and a known method such as a method of rotating and mixing a stirring blade or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic mixing may be appropriately selected.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and the temperature may be appropriately adjusted, but the temperature is preferably 15 to 30 °C.

When a solvent is used, it may be used by mixing any of the solvent and the solvent, and preliminarily diluting the formulation, or by dissolving any of the components other than the solvent, but by dissolving the solvent and the components. Mix and use.

The adhesive layer can be formed by applying an adhesive composition to the surface of the aforementioned support substrate and drying. At this time, the applied adhesive composition may be heated as needed to crosslink it.

The heating conditions can be, for example, 100 to 130 ° C for 1 to 5 minutes, but are not limited thereto. Further, the adhesive composition is applied onto the surface of the release layer of the release material and dried to form an adhesive layer, and the adhesive layer may be formed by bonding the adhesive layer to the surface of the support substrate and removing the release material. .

The adhesive composition may be applied to the surface of the support substrate or the surface of the release layer of the release material by a known method, and an air knife coater, a knife coater, a bar coater, or a gravure coat may be exemplified. Various coatings such as machine, roll coater, roll coater, curtain coater, die coater, knife coater, screen coater, bar coater, contact coater, etc. Machine method.

<Binder layer>

The layer of the agent then contains a dye. Unlike the pigment, the dye does not easily form agglomerates in the adhesive layer, and thus the above-mentioned cut grain bonded sheet maintains high quality.

The thickness of the adhesive layer can be appropriately selected depending on the purpose, but the thickness is preferably from 1 to 100 μm, more preferably from 5 to 75 μm, still more preferably from 5 to 50 μm.

In the present embodiment, unlike the case where a pigment is used as the coloring component, even when the thickness of the adhesive layer is, for example, about 10 μm or less, generation of aggregates in the adhesive layer can be suppressed, so that the finally obtained semiconductor can be suppressed. Cracks are formed in the package.

The color of the subsequent layer is not particularly limited as long as it is not the same as the color of the substrate (the above-mentioned adhesive substrate and non-adhesive substrate). However, since the annular frame tape is usually black, it is easy to distinguish from the annular frame tape. It is preferably a color other than black. Wherein, when the substrate is white, ΔE is in a preferable range, and it is easy to visually confirm the presence or absence of the adhesive layer in consideration of the above-described explanation, and the adhesive layer is preferably blue from the short wavelength side to the long wavelength side. The adhesive layer of any one of red colors, as such an adhesive layer, can be exemplified by L ^* (lightness) of 15 to 97 and a ^* (chromaticity) of -11~ in the L ^* a ^* b ^* color system. +15, and b ^* (chroma) is an adhesive layer of -30 to +5. Among them, the adhesive layer is preferably blue.

The content of the aforementioned dye in the subsequent layer is 8.3% by mass or less. Good is 8.1% by mass or less. Since it is the said range, the malfunction by containing a dye can be suppressed. More specifically, when a semiconductor package is manufactured using a dicing die bond sheet having an adhesive layer as described above, the obtained semiconductor package suppresses peeling or cracking at a joint portion between the substrate and the semiconductor wafer (package crack) ) and suppress the reduction in reliability. Further, when the adhesive substrate is used for cutting a die bond sheet, transfer of the dye from the adhesive layer to the adhesive layer can be suppressed.

When the ΔE to be described later becomes the target value, the lower limit of the dye content of the adhesive layer is not particularly limited. However, in view of the fact that it is easy to adjust ΔE to a preferable range, the aforementioned dye content of the adhesive layer is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and still more preferably 0.10% by mass or more.

The dye is not particularly limited as long as it is a dye which can color the adhesive layer in the above-described manner, and a known dye can be suitably used.

The dye may specifically be exemplified by an azo dye, a nitroso dye, a quinoline dye, a sulfur dye, a nitro dye, a methine dye, a polymethine dye, an aminoketone dye, a thiazole dye, a ketol dye, and a stilbene. Dyes, indamine dyes, indophenol dyes, diphenylmethane dyes, anthraquinone dyes, triarylmethane dyes, azine dyes, anthraquinone dyes, dibenzopyran dyes, oxazine dyes, thiazine dyes, hydrazines Cyan dye, acridine dye, etc.

The dye may be any of a water-soluble dye and a water-insoluble dye, but is preferably a water-insoluble dye, more preferably an oil-soluble dye.

The dye is preferably an azo dye having an azo group (-N=N-) in view of easy availability and easy adjustment of the adhesive layer to a target property.

The azo dye may also be a monoazo dye, a disazo dye, a trisazo dye, a tetrazo dye, and a polyazo dye (based on one molecule) depending on the number of azo groups in a molecule. Any one of the dyes having a number of azo groups of 5 or more is preferable, and a bisazo dye is preferable in view of facilitating formation of an adhesive layer which is relatively rigid in structure, high in heat resistance, and excellent in characteristics.

In view of further improving the reliability of the semiconductor package as described above and maintaining the adhesive layer with low conductivity, the dye is preferably such that the structure does not contain metal atoms or metal ions.

The color difference (ΔE) in the L ^* a ^* b ^* color system between the substrate and the adhesive layer is 30 to 53, preferably 31 to 52, more preferably 32 to 52.

Since ΔE is in the above range, it is easy to visually confirm the presence or absence of the adhesive layer described above.

More specifically, L ^* , a ^* , and b ^{* of the} base material and the adhesive layer were respectively calculated, and ΔE was calculated from the following formula (I).

△E=[(L1 ^* -L2 ^* ) ² +(a1 ^* -a2 ^* ) ² +(b1 ^* -b2 ^* ) ² ] ^1/2 ‧‧‧‧(I)

(In the formula, L1 ^* L ^* value of the substrate, L2 ^* L ^* value of the adhesive layer, a1 ^* is the base value of a ^*, a2 ^* is the adhesive layer of a ^* value, B1 ^* is the value of b ^* of the substrate, and b2 ^* is the value of b ^* of the adhesive layer.)

The subsequent layer preferably has pressure-sensitive adhesiveness or heat-hardening property, and more preferably has pressure-sensitive adhesiveness and heat curability. At the same time, the adhesive layer having pressure-sensitive adhesiveness and heat-hardening property can be attached to various adherends by light pressing in an uncured state. Further, the adhesive layer may be attached to various adherends by softening by heating. The subsequent agent layer is finally cured into a cured product having high impact resistance by thermal curing, and the cured product is excellent in shear strength, and can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

[Binder composition]

The adhesive composition may be formed by using an adhesive composition containing a constituent component of the adhesive layer such as the above-mentioned dye, and the content ratio of the nonvolatile components in the adhesive composition to the adhesive layer is also the same.

The adhesive layer is preferably formed using an adhesive composition containing a binder resin (a), an epoxy thermosetting resin (b), and the above dye (hereinafter referred to as "dye (s)").

(Binder resin (a))

The binder resin (a) is a polymer compound having a film forming property and flexibility in an adhesive layer.

The binder resin (a) may be used alone or in combination of two or more.

As the binder resin (a), an acrylic resin, a polyester resin, a urethane resin, an urethane acrylate resin, a polyoxyxylene resin, a rubber-based polymer, a phenoxy resin or the like can be used, and an acrylic resin is preferable. Resin.

A well-known acrylic polymer can be used for the said acrylic resin.

The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. If the weight average molecular weight of the acrylic resin is too small, the adhesion between the adhesive layer and the adhesive layer is increased, and pickup failure of the semiconductor wafer occurs. In addition, when the weight average molecular weight of the acrylic resin is too large, the adhesive layer cannot adhere to the uneven surface of the adherend, and it is a main cause of occurrence of voids and the like.

In the present specification, the weight average molecular weight means a polystyrene-converted value measured by a gel permeation chromatography (GPC) unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C. When the Tg of the acrylic resin is too low, the peeling force of the adhesive layer and the adhesive layer is increased to cause pickup failure of the semiconductor wafer. Moreover, if the Tg of the acrylic resin is too high, the adhesion force for fixing the semiconductor wafer may be insufficient.

Examples of the monomer constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl (meth)acrylate. An alkyl (meth) acrylate having an alkyl group such as a hexyl hexyl ester; a cycloalkyl (meth) acrylate, a benzyl (meth) acrylate, an isobornyl (meth) acrylate, (a) a group having a cyclic skeleton such as dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, or urethane (meth) acrylate. Acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (meth) acrylate containing a hydrocarbon group; (meth) acrylate A (meth) acrylate such as a glycidyl group-containing (meth) acrylate such as glycidyl ester.

Further, the acrylic resin may be a resin obtained by copolymerizing a monomer such as acrylic acid, methacrylic acid, methylene succinic acid, vinyl acetate, acrylonitrile, styrene or N-methylol acrylamide.

The monomer constituting the acrylic resin may be one type or two or more types.

In addition, in the present specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid", and "(meth)acrylate" includes "acrylic acid ester" and "methacrylic acid". Ester" the concept of both.

The acrylic resin may have a functional group which may be bonded to another compound such as a vinyl group, a (meth) acrylonitrile group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group. It can be bonded to other compounds via a crosslinking agent (f) described later. Alternatively, the aforementioned functional groups may be directly bonded to other compounds without passing through the crosslinking agent (f). The acrylic resin is bonded by the above-described functional groups, whereby the reliability of the semiconductor package using the above-described diced die bonding sheet tends to be improved.

In the solid content of the composition of the second embodiment, the content of the acrylic resin is preferably 50% by mass or more. Thereby, when the adhesive layer is used in the batch hardening process at the time of resin sealing of a semiconductor wafer, an adhesive layer becomes a preferable property. The reason for this is that in the above process, the wafer is subjected to wire bonding before the semiconductor wafer is resin-sealed, but the adhesive layer before curing is exposed to a high temperature to ensure a certain degree of hardness. The state is wire bonded. That is, when the content of the acrylic resin in the adhesive composition is large, the storage modulus of the adhesive layer can be improved before thermal curing. Therefore, even when the adhesive layer is not cured or semi-hardened, the vibration and displacement of the wafer during wire bonding can be suppressed, so that wire bonding can be stably performed.

Further, in the solid content of the adhesive composition, the content of the acrylic resin is more preferably from 50 to 85% by mass. When the content of the acrylic resin is in the above range, the pick-up property of the semiconductor wafer is improved.

In the present invention, in order to improve the peelability of the adhesive layer and to improve the pick-up property, or to prevent the occurrence of voids or the like by adhering the adhesive layer to the uneven surface of the adherend, (a) the adhesive resin may be used alone. A thermoplastic resin other than an acrylic resin (hereinafter simply referred to as "thermoplastic resin"), It can be used together with acrylic resin.

The thermoplastic resin preferably has a weight average molecular weight of from 1,000 to 100,000, more preferably a weight average molecular weight of from 3,000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably from -30 to 150 ° C, more preferably from -20 to 120 ° C.

The thermoplastic resin may, for example, be a polyester resin, a urethane resin, a phenoxy resin, polybutene, polybutadiene, polystyrene or the like.

The above thermoplastic resins may be used alone or in combination of two or more.

The effect as described above can be obtained by using the aforementioned thermoplastic resin, but on the other hand, the hardness of the adhesive layer before curing is lowered at a high temperature, and the wire bonding suitability of the adhesive layer is in an unhardened or semi-hardened state. There is a reduction in ambiguity. Therefore, it is preferable to set the content of the acrylic resin of the adhesive composition after considering the above influence.

(epoxy thermosetting resin (b))

The epoxy thermosetting resin (b) contains an epoxy resin and a thermosetting agent.

The epoxy-based thermosetting resin (b) may be used alone or in combination of two or more.

The epoxy resin may, for example, be a known epoxy resin, and specific examples thereof include a polyfunctional epoxy resin, a biphenyl compound, a bisphenol A diglycidyl ether and a hydrogenated product thereof, an o-cresol novolac epoxy resin, and a bicyclic ring. Pentadiene ring A bifunctional or higher epoxy compound such as an oxygen resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenyl skeleton type epoxy resin.

Further, as the epoxy resin, an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group may be a compound obtained by changing a part of the epoxy resin of the polyfunctional epoxy resin to a group containing an unsaturated hydrocarbon group. The above compound can be produced, for example, by an addition reaction of acrylic acid and an epoxy group. In addition, as the epoxy resin having an unsaturated hydrocarbon group, a compound obtained by directly bonding a group containing an unsaturated hydrocarbon group to an aromatic ring constituting an epoxy resin or the like can be exemplified. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically, a vinyl group, a 2-propenyl (propylene group), an acryl fluorenyl group, a methacryl fluorenyl group, an acrylamide group, a methyl group can be exemplified. The acrylamide group or the like is preferably an acrylonitrile group.

The compatibility between the epoxy resin having an unsaturated hydrocarbon group and the acrylic resin is higher than that of the epoxy resin having no unsaturated hydrocarbon group. Therefore, the packaging reliability of the semiconductor device can be improved by using an adhesive composition containing an epoxy resin having an unsaturated hydrocarbon group.

The epoxy resin is preferably a softening point or a glass transition temperature higher in view of improving the pick-up property.

The number average molecular weight of the epoxy resin is not particularly limited, but from the viewpoints of the hardenability of the adhesive layer or the strength and heat resistance after curing. Look, preferably 300~30000, more preferably 400~10000, especially 500~3000.

The epoxy resin preferably has an epoxy equivalent of from 100 to 1000 g/eq, more preferably from 300 to 800 g/eq.

These epoxy resins may be used alone or in combination of two or more.

The function of the aforementioned heat hardener is a hardener for hardening an epoxy resin.

The thermosetting agent can be exemplified by a compound having two or more functional groups reactive with an epoxy group in one molecule. The functional group may, for example, be a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group or an acid group, and is preferably a phenolic hydroxyl group, an amine group or an acid group. A phenolic hydroxyl group or an amine group is particularly preferably a phenolic hydroxyl group.

The phenolic curing agent (hardener having a phenolic hydroxyl group) in the above-mentioned thermosetting agent may, for example, be a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, or an aralkyl phenol resin. .

The amine-based curing agent (hardening agent having an amine group) in the above-mentioned thermosetting agent can be exemplified by DICY (dicyandiamide) or the like.

The aforementioned thermal hardener may also have an unsaturated hydrocarbon group.

The thermosetting agent having an unsaturated hydrocarbon group may, for example, be a compound obtained by substituting a part of a hydroxyl group of a phenol resin containing a group of an unsaturated hydrocarbon group, or an aromatic ring directly bonded to a phenol resin by a group containing an unsaturated hydrocarbon group. Compounds, etc. The unsaturated hydrocarbon group in the heat hardener is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

In view of improving the pick-up property, the aforementioned heat hardener is preferably a softening point or a glass transition temperature.

The number average molecular weight of the above-mentioned thermosetting agent is preferably from 300 to 30,000, more preferably from 400 to 10,000, still more preferably from 500 to 3,000.

These thermosetting agents may be used alone or in combination of two or more.

The content of the thermal curing agent in the composition of the second embodiment is preferably from 0.1 to 500 parts by mass, more preferably from 1 to 200 parts by mass, per 100 parts by mass of the epoxy resin. When the content of the thermosetting agent is too small, the adhesion cannot be obtained due to insufficient curing, and if the content of the thermosetting agent is excessive, the moisture absorption rate of the adhesive layer is increased to lower the package reliability.

The content of the epoxy-based thermosetting resin (b) (the total content of the epoxy resin and the thermosetting agent) of the adhesive composition is preferably from 1 to 100 parts by mass based on 100 parts by mass of the binder resin (a). More preferably, it is 1.5 to 75 parts by mass, and particularly preferably 2 to 60 parts by mass. Since the content of the epoxy-based thermosetting resin (b) is in the above range, the hardness of the adhesive layer before curing is maintained, and the adhesion of the adhesive layer in the unhardened or semi-cured state is improved. Moreover, the easy pick-up property of the semiconductor wafer is improved.

(dye(s))

The dye (s) is as previously described.

The content of the dye (s) in the solid content of the subsequent composition is preferably the same as the dye content of the adhesive layer described above.

In order to improve various physical properties of the adhesive layer, an adhesive composition may be used to form an adhesive layer which contains a binder resin (a), an epoxy thermosetting resin (b), and a dye (s). Further, other ingredients than the aforementioned ingredients are contained as needed.

The other components contained in the composition of the second embodiment are preferably an inorganic filler (c), a curing accelerator (d), a coupling agent (e), a crosslinking agent (f), or an epoxy thermosetting resin (b). Other thermosetting resins (g), general additives (h), and the like.

(Inorganic Filling Material (c))

The subsequent composition is easy to adjust the thermal expansion coefficient by further containing the inorganic filler (c), and the thermal expansion coefficient of the cured adhesive layer is optimized for the semiconductor wafer or the metal or the organic substrate, thereby improving the package. reliability.

Further, the adhesive composition can reduce the moisture absorption rate of the adhesive layer after curing by further containing the inorganic filler (c).

As a preferred inorganic filler (c), cerium oxide, a powder of alumina, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, boron nitride or the like; beads obtained by spheroidizing the above-mentioned cerium oxide; surface modification of the above-mentioned cerium oxide; Single crystal fiber such as enamel; glass fiber, and the like.

Among them, the inorganic filler (c) is preferably a cerium oxide filler, an alumina filler or a surface modification of the materials.

The inorganic filler (c) may be used alone or in combination of two or more.

When the inorganic filler (c) is used, the content of the inorganic filler (c) in the solid content of the adhesive composition is preferably from 1 to 80% by mass.

(hardening accelerator (d))

The hardening accelerator (d) is used to adjust the hardening speed of the adhesive composition.

Preferred hardening accelerators (d) are exemplified by tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl An imidazole such as imidazole (an imidazole in which one or more hydrogen atoms are substituted by a group other than a hydrogen atom); an organic phosphine such as tributylphosphine, diphenylphosphine or triphenylphosphine (one or more hydrogen atoms are replaced by an organic group) a phosphine formed; tetraphenylboron such as tetraphenylboron tetraphenylphosphine or tetraphenylboron triphenylphosphine.

The hardening accelerator (d) may be used singly or in combination of two on.

When the curing accelerator (d) is used, the content of the curing accelerator (d) in the adhesive composition is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the epoxy-based thermosetting resin (b). More preferably, it is 0.1 to 1 part by mass. By setting the content of the hardening accelerator (d) to the above range, the adhesive layer has excellent adhesion characteristics even under high temperature and high humidity conditions, and high package reliability can be achieved even when exposed to strict reflow conditions. Sex. When the content of the hardening accelerator (d) is too small, the effect of using the curing accelerator (d) cannot be sufficiently obtained, and if the content of the curing accelerator (d) is excessive, the high-polarity hardening accelerator (d) Under high temperature and high humidity conditions, it will be segregated in the adhesive layer toward the interface side of the adherend, thereby deteriorating the package reliability.

(Coupling agent (e))

The coupling agent (e) has a functional group reactive with an inorganic compound and a functional group reactive with the organic functional group, and the adhesion and adhesion of the adhesive layer to the adherend can be achieved by using the coupling agent (e). improve. Further, the cured product obtained by curing the adhesive layer by using the coupling agent (e) can improve the water resistance without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group having a binder resin (a) or an epoxy thermosetting resin (b), and is preferably a decane coupling agent.

Preferably, the aforementioned decane coupling agent is exemplified by γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, and β-(3,4-epoxycyclohexyl). Ethyltrimethoxydecane, γ-(methacryloxypropyl)trimethoxydecane, γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)-γ-aminopropyl Trimethoxy decane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-ureido Propyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfane, methyl Trimethoxy decane, methyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

The coupling agent (e) may be used alone or in combination of two or more.

When the coupling agent (e) is used, the content of the coupling agent (e) of the adhesive composition is preferably 100 parts by mass based on 100 parts by mass of the total of the binder resin (a) and the epoxy-based thermosetting resin (b). ~20 parts by mass, more preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass. If the content of the coupling agent (e) is too small, the above-described effect of using the coupling agent (e) cannot be obtained, and if the content of the coupling agent (e) is too large, outgassing may occur.

(crosslinking agent (f))

When the acrylic resin having a functional group capable of bonding with another compound such as an isocyanate group is used as the binder resin (a), the crosslinking group (f) can be used to bond and crosslink the functional group with other compounds. . The initial adhesion and cohesive force of the adhesive layer can be adjusted by crosslinking with a crosslinking agent (f).

The crosslinking agent (f) can be exemplified by an organic polyvalent isocyanate compound, an organic polyimine compound, and the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and terpolymers, isocyanurate compounds, and adducts of the compounds. a reaction product of a low molecular weight active hydrogen-containing compound such as an alcohol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, such as trimethylolpropane-added xylene diisocyanate, or an organic polyisocyanate compound A terminal isocyanate urethane prepolymer obtained by reacting a polyol compound.

More specifically, the aforementioned organic polyisocyanate compound is exemplified by 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, and diphenylmethane- 4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane -4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, addition of toluene diisocyanate or hexamethylene diisocyanate to all or part of the hydrocarbon group of a polyol such as trimethylolpropane The compound, diazonic acid diisocyanate or the like.

The above organic polyimine compound can be exemplified by N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine propionic acid. Ester, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tri-ethyl melamine, and the like.

When an isocyanate type crosslinking agent is used as the crosslinking agent (f), it is preferred to use a polymer having a hydroxyl group as the acrylic resin of the binder resin (a). When the crosslinking agent (f) has an isocyanate group and the acrylic resin has a hydroxyl group, the crosslinking structure can be easily introduced into the adhesive layer by the reaction of the crosslinking agent (f) with the acrylic resin.

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the binder resin (a). It is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass.

(Other thermosetting resins (g))

The other thermosetting resin (g) may be other than the epoxy resin in the epoxy thermosetting resin (b), and examples thereof include a thermosetting polyimide resin, a polyurethane resin, an unsaturated polyester resin, and a polyfluorene. Oxygen resin, etc.

(General additive (h))

The general-purpose additive (h) can be exemplified by a known plasticizer, an antistatic agent, an antioxidant, a pigment, a dye, a getter, and the like.

(solvent)

The composition of the subsequent agent further contains a solvent, and the workability is improved by dilution.

The solvent contained in the composition of the second embodiment is not particularly limited, but preferred examples of the solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol and isobutanol (2-methylpropan-1-ol). An alcohol such as 1-butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; a decylamine such as dimethylformamide or N-methylpyrrolidone (a compound having a guanamine bond); .

The solvent contained in the subsequent composition may be one type or two or more types.

In view of uniformly mixing the components used in the adhesive composition, the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like.

The subsequent composition is obtained by blending a dye (s) and an adhesive layer constituent component other than the dye (s).

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

The method of mixing the components at the time of preparation is not particularly limited, and a known method such as a method of rotating and mixing a stirring blade or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic mixing may be appropriately selected.

The temperature and time when the respective components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 °C.

When a solvent is used, it may be used by mixing any of the solvent and the solvent, and preliminarily diluting the compounding component, or by mixing the solvent and the compounding component without previously diluting any of the components other than the solvent. use.

The subsequent layer can be formed using the adhesive composition and in the same manner as described above for forming the adhesive layer on the support substrate. However, when the aforementioned adhesive substrate is used, it is generally difficult to apply the adhesive composition directly to the adhesive layer. Therefore, for example, the adhesive composition is applied to the surface of the release layer of the release material and dried to form an adhesive layer, and the adhesive layer is bonded to the surface of the adhesive layer to remove the release material or the like. The method of attaching the adhesive to the surface of the adhesive layer.

[Examples]

The invention will be described in more detail below on the basis of specific examples. However, the invention is not limited to the embodiments shown below.

<Manufacture of Cut Grain Bonding Sheet>

[Examples 1 to 6 and Comparative Examples 1 to 2]

(Manufacture of adhesive composition)

Each component was blended in the amounts shown in Table 1, and further diluted with methyl ethyl ketone to obtain an adhesive composition.

The short codes of the components in Table 1 have the following meanings, respectively.

‧Binder resin (a)

(a)-1: Acrylic resin (manufactured by TOYOCHEM Co., Ltd., weight average molecular weight: 500,000, glass transition temperature: 9 ° C, methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 Mass parts)

‧Epoxy thermosetting resin (b)

(b)-11: a cresol novolac type epoxy resin having an acrylonitrile group ("CNA-147" manufactured by Nippon Kayaku Co., Ltd.)

(b)-21: Aralkyl phenol resin ("MILEX XLC-4L" manufactured by Mitsui Chemicals, Inc.)

‧Filling material (c)

(c)-1: methacrylonitrile-based modified filler ("SO-C2" manufactured by ADMATECHS Co., Ltd., average particle diameter of 0.5 μm, 3-methylpropoxypropyltrimethoxydecane of cerium oxide Processing product)

‧Coupling agent (e)

(e)-1: decane coupling agent ("MKC Silicate MSEP2" manufactured by Mitsubishi Chemical Corporation))

‧ Crosslinking agent (f)

(f)-1: Aromatic polyisocyanate ("CORONATE L" manufactured by Japan Polyurethane Industrial Co., Ltd., toluene diisocyanate trimer adduct of trimethylolpropane)

‧Dye (s)

(s)-1: Solvent Black 3 ("OIL Black 860" manufactured by Oriental Chemical Industry Co., Ltd., oil-soluble disazo dye)

(s)-2: Solvent Red 18 ("Red TR-71" manufactured by Central Synthetic Chemical Co., Ltd., oil-soluble disazo dye)

(Manufacture of cut die bond sheets)

The peeling treatment surface of the release sheet which was subjected to the release treatment on one side of the polyethylene terephthalate film was coated with the obtained adhesive composition, and dried at 120 ° C for 3 minutes, thereby forming a thickness of 5 μm or 20 μm of the adhesive layer. Further, the same release sheet as described above was bonded to the adhesive layer to prepare two non-carrier films having a thickness of the adhesive layer of 5 μm and 20 μm.

Next, a non-carrier film having a thickness of the adhesive layer of 20 μm in the non-carrier film was used, and one of the release sheets was peeled off, and the adhesive layer was transferred to a dicing tape (G-562, manufactured by LINTEC). On the adhesive layer, a cut die bond is obtained. Further, the substrate of the dicing tape is white and the adhesive layer is colorless.

<Evaluation of Cutting Grain Bonding Sheet>

With respect to the diced die-bonding sheet obtained as described above, the visibility of the adhesive layer and the reliability of the semiconductor package were evaluated by the following methods.

(Color difference (ΔE) between the substrate and the adhesive layer)

The dicing tape ("G-562" manufactured by Linde Co., Ltd.) was measured using a spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by SHIMADZU Co., Ltd.), and The light transmittance of the adhesive layer having a thickness of 5 μm as described above. Further, the light transmittance of the dicing tape was measured from the side of the adhesive layer. At this time, the measurement was performed using the large sample chamber MPC-3100 attached to the spectrophotometer without using the built-in integrating sphere.

Then, based on the measurement results of the obtained light transmittance, L ^* , a ^* , and b ^* of the dicing tape and the adhesive layer as the base material were respectively calculated in accordance with JIS Z 8781-4:2013, and the color difference was calculated according to the above formula (I). (△E). The results are shown in Table 1. The L ^* , a ^* , and b ^{* of the} adhesive layer are collectively shown in Table 1. Further, the dicing tape had an L ^* of 46, a ^* of 1.6, and b ^* of -2.9.

(visual confirmation of the adhesive layer)

Using a tape bonding machine ("Adwill RAD 2500" manufactured by Linde Co., Ltd.), the diced die-bonding sheets having a thickness of the adhesive layer of 20 μm in the dicing die-bonding sheets of the examples and the comparative examples were pasted via the adhesive layer thereof. It is attached to a polished surface of a dry-polished silicon wafer (having a diameter of 150 mm and a thickness of 75 μm), and the germanium wafer is fixed to a ring frame for wafer cutting. Next, the wafer was cut into a size of 8 mm × 8 mm using a dicing apparatus ("DFD651" manufactured by DISCO Corporation) to obtain a wafer. This cutting was performed by cutting the substrate into the substrate at a thickness of 20 μm.

The wafer to which the dicing die bonding sheet is attached and the adhesive layer dicing the die bonding sheet are collectively picked up from the substrate. Then, a copper foil (thickness: 18 μm) in a copper foil laminated laminate ("CCL-HL830" manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used to form a circuit pattern on the circuit pattern. A substrate with a solder resist ("PSR-4000 AUS303" manufactured by Sun Ink Co., Ltd.) ("LN001E-001 PCB (Au) AUS303" manufactured by CHINO GIKEN) is laminated at 120 ° C, 2.45 N (250 gf), 0.5 second. Under the condition, the wafer with the adhesive layer described above is pressure-bonded to the substrate via the adhesive layer. Further, using the dicing die-bonding sheet having a thickness of the adhesive layer of 5 μm in the dicing die-bonding sheet obtained as described above, after the wafer was obtained in the same order as described above, the wafer and the diced die-bonding sheet were picked up from the substrate. The adhesive layer is further crimped via the adhesive layer to the wafer that has been crimped onto the substrate. In this process, the color of the adhesive layer seen between the annular frame and the wafer and the color of the picked-up portion of the wafer with the adhesive layer are visually observed to confirm whether the colors can be clearly recognized by visual observation. Whether they are different from each other, that is, whether the adhesive layer is transferred to the wafer. The results are shown in Table 1. In Table 1, "Yes" indicates that it can be clearly identified by visual observation, and "No" indicates that it cannot be clearly identified by visual observation.

(reliability of semiconductor package)

The laminate of the substrate and the wafer with the adhesive layer prepared at the time of visual confirmation of the evaluation of the adhesive layer was heated at 175 ° C for one hour using an oven. Then, the laminate was taken out from the oven and cooled to room temperature, and a compression resin ("KE-1100AS3" manufactured by Kyocera Chemical Co., Ltd.) and a sealing device ("MPC-06M TriAl Press" manufactured by APIC YAMADA Co., Ltd.) were used to seal the thickness. The laminate was sealed in a manner of 400 μm, and heated at 175 ° C for 5 hours, whereby the above-mentioned stamper resin was cured. Then, the sealed laminate was attached to a dicing tape ("Adwill D-510T" manufactured by Linde Co., Ltd.), and cut into a size of 8 mm × 8 mm using a cutting device ("DFD651" manufactured by DISCO Corporation). A semiconductor package for evaluating reliability is obtained.

The semiconductor package obtained above was placed at 85 ° C and a relative humidity of 60% for 168 hours, and after moisture absorption, a reflow furnace ("WL-15-20DNX type" manufactured by Sagami Polytec Co., Ltd.) was used. Three times of IR reflow was performed under the conditions of a maximum heating temperature of 260 ° C and a heating time of one minute.

Then, in the semiconductor package for IR reflow, whether the joint portion of the cross-section observation substrate and the semiconductor wafer was floated or peeled off, and the peeling was observed at 0.5 mm or more in the joint portion, and the peeling was determined for 25 semiconductor packages. Count the number of unpacked semiconductor packages. In the semiconductor package for IR reflow, a scanning ultrasonic flaw detector ("Hye-Focus" manufactured by Hitachi Construction Machinery FINE TECH Co., Ltd.) was used to confirm the presence or absence of a package crack. The results are shown in Table 1. In Table 1, "No" indicates that no package crack has occurred, and "Yes" indicates that a package crack has occurred.

As a result, it was found that the adhesive layer of the dicing die-bonding sheets of Examples 1 to 6 contained the dye in an amount of 0.1 to 8.3% by mass. Therefore, ΔE was in a specific range, and the adhesive layer was excellent in visual confirmation and obtained. The reliability of semiconductor packages is also improved.

On the other hand, in the adhesive layer of the diced die-bonding sheet of Comparative Example 1, the dye was not contained, and therefore ΔE was outside the specific range, and the visibility of the adhesive layer was poor.

Further, even if the adhesive layer of the diced die-bonding sheet of Comparative Example 2 contains a dye, ΔE is outside the specific range, and the visibility of the adhesive layer is not good. Further, since the amount of the dye contained in the adhesive layer is too large, a large amount of peeling is observed in the joint portion between the substrate and the semiconductor wafer of the obtained semiconductor package, and a package crack is also generated, which is low in reliability.

[Industrial availability]

The invention can be used to fabricate semiconductor wafers and the like.

Claims (3)

A dicing die bonding sheet comprising a dye-containing adhesive layer on a substrate; the dye content of the adhesive layer is 8.3% by mass or less; and L ^* a ^* between the substrate and the adhesive layer b ^{* The} color difference in the color system is 30~53. The diced die bond sheet of claim 1, wherein the dye is a disazo dye. The diced die bond sheet of claim 1 or 2, wherein the dye has no metal atom or metal ion in its configuration.