TWI664667B - Dicing die-bonding sheet - Google Patents

Abstract

A dicing die-bonding sheet comprising an adhesive layer containing a dye on a substrate, the content of the dye in the adhesive layer being 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.

Description

Cutting die bond sheet

The present invention relates to a dicing die-bonding sheet having an adhesive layer on a substrate.

This application claims priority based on Japanese Patent Application No. 2014-253241 filed in Japan on December 15, 2014, and the content is incorporated into this application.

A dicing die-bonding sheet formed with an adhesive layer on a substrate is used for cutting from a semiconductor wafer and picking it up through the semiconductor wafer until the picked-up semiconductor wafer is bonded to a substrate, a lead frame, or other semiconductor wafers. The steps.

The adhesive layer in the above-mentioned sheet is usually colorless and transparent. Therefore, it is difficult to check whether the adhesive layer is adhering to the semiconductor wafer or semiconductor when the sheet is subjected to precut processing or die bonding of the semiconductor wafer. The state of the wafer and the like following the object. If the adhesive layer is not adhered to a desired portion, problems may occur in the manufacturing steps of the semiconductor device. In addition, when the adhesive layer is cut by invisible cutting or cold expansion, the Since the adhesive layer is colorless and transparent, it cannot be easily confirmed whether or not the adhesive layer has been definitely cut off, and thus the manufacturing efficiency of the semiconductor device is reduced.

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

Among them, as an adhesive layer that can be easily inspected, an adhesive layer containing a pigment that absorbs or reflects light in a wavelength range of 290 to 450 nm has been disclosed (see Patent Document 1).

Since such an adhesive layer is colored because it contains a pigment, the presence or absence of this adhesive layer can be easily confirmed visually.

[Prior technical literature]

[Patent Literature]

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

However, the adhesive layer described in Patent Document 1 has the following problems: Because it contains a pigment, when the thickness is thin, agglomerates or color unevenness may be generated, and cracks may be generated in the finally obtained semiconductor package. Reduced reliability.

The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a dicing die-bonding sheet that can easily confirm the presence or state of an adhesive layer, and can obtain a highly reliable semiconductor package.

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

In the dicing die-bonding 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 that does not include metal atoms or metal ions in the structure.

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

<< Cut Die Bonding Sheet >>

The dicing die-bonding sheet according to this embodiment is characterized in that an adhesive layer containing a dye is provided on a substrate, 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 L ^* a ^* b ^* color difference (hereinafter abbreviated as "△ E") in the color system is 30 to 53.

In the present specification, the aforementioned L ^* , a ^*, and b ^{* are} calculated based on JISZ8781-4: 2013.

Since the adhesive layer of the dicing die-bonding sheet contains a specific amount of dye, the color difference (ΔE) is within a specific range. As a result, whether or not the dicing die-bonding sheet has an adhesive layer can be easily confirmed.

In addition, by using the above-mentioned dicing die-bonding sheet, when the dicing die-bonding sheet is subjected to standard cutting processing, or when a semiconductor wafer is picked up or die-bonded, it can be easily visually confirmed whether the adhesive layer is bonded to the semiconductor. The state of the adhered object, such as a wafer or a semiconductor wafer, can suppress problems in the manufacturing process of the semiconductor device.

In addition, by using the dicing die-bonding sheet described above, in the process of manufacturing a semiconductor wafer, it is possible to easily confirm whether the adhesive layer is definitely cut even when performing invisible dicing, so that the manufacturing efficiency of the semiconductor device can be suppressed. The so-called stealth dicing is to form a fragile part inside the wafer by laser irradiation, and to cut the dicing die bonding sheet to which the aforementioned wafer is attached. The wafer is expanded and the wafer is cut.

In addition, even when the so-called cold expansion is performed, that is, when the adhesive layer that forms the brittle portion at a low temperature is expanded and cut, it is easy to visually confirm whether the adhesive layer has been surely cut, as in the case of invisible cutting. This state can suppress a decrease in the manufacturing efficiency of the semiconductor device.

Usually, when the expansion is performed, whether the adhesive layer has been cut is confirmed by visual observation or observation with a microscope. However, according to the present invention, it is easy to visually confirm the adhesive layer, so it can be confirmed in a short time. If the adhesive layer is not cut, when the target wafer is picked up, the surrounding wafers will also be lifted at the same time, causing problems.

Furthermore, 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 using the dicing die bond sheet described above suppresses cracks or peeling of 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, agglomerates or color unevenness may sometimes occur in the adhesive layer. Cracks occur in semiconductor packages, 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 it is usually preferably white.

The substrate may be provided with an adhesive layer on the surface (hereinafter sometimes referred to as "adhesive substrate", and the substrate in contact with the adhesive layer in this case is referred to as "supporting substrate"), or it may not have an adhesive layer (hereinafter referred to as (Referred to as "non-adhesive substrate").

When the substrate is the aforementioned adhesive substrate, the laminated structure of the supporting substrate and the 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 supporting substrate is preferably various resins. Specifically, examples thereof include polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE). Etc.)), polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, poly Urethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionic polymer resin, ethylene / (meth) acrylic copolymer, ethylene / (meth) acrylate copolymer , Polystyrene, polycarbonate, fluororesin, hydride, modified product, crosslinked product or copolymer of any of these resins.

The aforementioned non-adhesive substrate and supporting substrate may include one layer (single layer) or a plurality of layers. When a plurality of layers are included, the material of each layer may be the same or different, or only part of the same. .

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

The aforementioned non-adhesive substrate and supporting substrate may be subjected to embossing treatment such as sandblasting treatment, solvent treatment, or corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromium Oxidation treatment, such as acid treatment and hot air treatment, etc., can improve the adhesion with the layer provided above it, that is, with the adhesive layer or the adhesive layer. In addition, the non-adhesive substrate and the support substrate may be a non-adhesive substrate and a support substrate that have been surface-primed.

Among them, in consideration of suppressing the fracture of the substrate due to scraper friction during cutting, the aforementioned non-adhesive substrate and supporting substrate are particularly preferably subjected to an electron beam irradiation treatment on the surface.

[Adhesive layer]

As said adhesive layer, a well-known adhesive layer can be used suitably. When the adhesive layer is colorless, the aforementioned adhesive substrate will reflect the color of the supporting substrate, and when the adhesive layer is colored (colored), the aforementioned adhesive substrate will reflect the color of the adhesive layer, or the supporting substrate and the adhesive layer Colors on both sides.

The adhesive layer can be formed using an adhesive composition, and the aforementioned adhesive composition contains various constituent components of the adhesive layer. The content ratio of the non-volatile components in the adhesive composition to each other is also the same in the adhesive layer.

When the adhesive layer contains a component polymerized by irradiation with energy rays, The semiconductor wafer is picked up by reducing the adhesion by irradiating the energy rays. For example, such an adhesive layer can be formed using various adhesive compositions containing an energy ray polymerizable acrylic polymer, and the energy ray polymerizable acrylic polymer is polymerized by energy ray irradiation.

Examples of the preferable adhesive composition include an adhesive composition (adhesive composition (i)) containing the aforementioned acrylic polymer and an energy ray polymerizable compound, and acrylic polymer having a hydroxyl group and a polymerizable group in a branched chain. An adhesive composition (such as an acrylic polymer having a hydroxyl group and a polymerizable group in a branched chain via a urethane bond) and an isocyanate-based crosslinking agent (adhesive composition (ii)), more preferably It further contains a solvent.

The adhesive composition may further contain any of various additives such as a photopolymerization initiator, or a dye, a pigment, an antidegradant, an antistatic agent, a flame retardant, a polysiloxane, and a chain transfer agent in addition to the aforementioned components. One.

The thickness of the adhesive layer can be appropriately selected according to the purpose, but the thickness is preferably 1 to 100 μm, more preferably 1 to 60 μm, and even more preferably 1 to 30 μm.

The adhesive composition is obtained by, for example, 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 simultaneously.

There is no particular limitation on the method of mixing the components during mixing, and a known method such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, or a method of applying ultrasonic mixing can be appropriately selected.

The temperature and time for adding and mixing the components are not particularly limited as long as the components are not deteriorated, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

When a solvent is used, the solvent can be used by mixing the solvent with any of the formulation ingredients other than the solvent and diluting the formulation ingredient in advance, or by not diluting any formulation ingredient other than the solvent in advance, but by mixing the solvent with the formulation ingredients Mix and use.

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

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

What is necessary is just to apply an adhesive composition to the surface of a support base material or the surface of the release layer of a release material by a well-known method, and an air knife coater, a knife coater, a rod coater, and a gravure coat can be illustrated. Machine, roll coater, roll knife coater, curtain coater, mold coater, knife coater, screen coater, wire rod coater, contact coater, etc. Machine method.

<Adhesive layer>

The adhesive layer contains a dye. Unlike dyes and pigments, agglomerates are not likely to be generated in the adhesive layer, so the aforementioned dicing die-bonding sheet maintains high quality.

The thickness of the adhesive layer can be appropriately selected according to the purpose, but the thickness is preferably 1 to 100 μm, more preferably 5 to 75 μm, and even more preferably 5 to 50 μm.

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

The color of the adhesive 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), but the ring-shaped frame tape is usually black. , Preferably a color other than black. Among them, when the substrate is white, ΔE is in a preferable range. Considering the easy-to-see visual existence and state of the adhesive layer described above, the adhesive layer is preferably blue from the short wavelength side to the long wavelength side ~ An adhesive layer of any color in red. Examples of such an adhesive layer include L ^* a ^* b ^* L ^* (lightness) in the color system is 15 to 97, and a ^* (chroma) is -11 to +15, and b ^* (chromaticity) is an adhesive layer of -30 to +5. Among them, the adhesive layer is preferably blue.

The content of the dye in the adhesive layer is 8.3% by mass or less. It is preferably 8.1% by mass or less. Since it is in the said range, the disadvantage caused by containing a dye can be suppressed. More specifically, when a semiconductor package is manufactured using a dicing die-bonding sheet having an adhesive layer as described above, the obtained semiconductor package suppresses peeling or cracks (sealing of the package) from the joint between the substrate and the semiconductor wafer. ), And suppress the decrease in reliability. Moreover, when the said adhesive base material is used for a dicing die-bonding sheet, transfer of a dye from an adhesive layer to an adhesive layer can be suppressed.

The lower limit of the content of the dye in the adhesive layer is not particularly limited as long as ΔE described later is a target value. However, considering that it is easy to adjust ΔE to a preferable range, the content of the dye in the adhesive layer is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and even more preferably 0.10% by mass or more.

The dye is not particularly limited insofar as it does not affect the effects of the present invention as long as the dye can color the adhesive layer in the manner described above, and a known dye can be appropriately used.

Specific examples of the dye include azo dye, nitroso dye, quinoline dye, sulfur dye, nitro dye, methine dye, polymethine dye, amino ketone dye, thiazole dye, keto alcohol dye, and stilbene Dyes, indamine dyes, indophenol dyes, diphenylmethane dyes, anthraquinone dyes, triarylmethane dyes, azine dyes, indigo dyes, dibenzopiperan dyes, oxazine dyes, thiazine dyes, phthalates Cyan dye, acridine dye, etc.

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

In view of easy availability and easy adjustment of the adhesive layer to target characteristics, the aforementioned dye is preferably an azo dye having an azo group (-N = N-).

According to the number of azo groups in a molecule, the aforementioned azo dyes can also be monoazo dyes, disazo dyes, triazo dyes, tetraazo dyes, and polyazo dyes (have in one molecule Any of the dyes having an azo group of 5 or more) is a disazo dye, in view of the ease of forming an adhesive layer having a relatively rigid structure, higher heat resistance, and good characteristics.

In view of further improving the reliability of the semiconductor package as described above and maintaining low conductivity of the adhesive layer, it is preferable that the dye does not include metal atoms or metal ions in the structure.

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

Since ΔE is within the aforementioned range, it is easy to visually confirm the presence and state of the adhesive layer described above.

More specifically, L ^* , a ^* , and b ^{* of} a base material and an adhesive layer are computed, respectively, and (DELTA) E is computed from 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 adhesive layer preferably has pressure-sensitive adhesiveness or heat-hardening properties, and more preferably has both pressure-sensitive adhesiveness and heat-hardening properties. The adhesive layer having both pressure-sensitive adhesiveness and heat-curing properties can be attached to various adherends by lightly pressing in an uncured state. In addition, the adhesive layer can be softened by heating and attached to various adherends. The adhesive layer is finally hardened with high impact resistance through thermal hardening. The hardened material has excellent shear strength and maintains sufficient bonding properties even under severe high temperature and high humidity conditions.

[Adhesive composition]

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

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

(Binder Resin (a))

The binder resin (a) is a polymer compound that makes the adhesive layer have film-forming properties and flexibility.

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

As the binder resin (a), acrylic resin, polyester resin, urethane resin, urethane acrylate resin, silicone resin, rubber polymer, phenoxy resin, etc. can be used, and acrylic resin is preferred. Resin.

As the acrylic resin, a known acrylic polymer can be used.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 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, which may cause pick-up failure of the semiconductor wafer. In addition, if 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 becomes a main cause of pores and the like.

In addition, in this specification, unless otherwise stated, a weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, and more preferably -30 to 50 ° C. If the Tg of the acrylic resin is too low, the peeling force between the adhesive layer and the adhesive layer increases, which may cause poor pick-up of the semiconductor wafer. Further, if the Tg of the acrylic resin is too high, the adhesive 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. Alkyl (meth) acrylates having 1 to 18 carbon atoms in alkyl groups such as hexyl ester; cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (formyl) (Meth) acrylate having a cyclic skeleton, such as dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl ethoxylate (meth) acrylate, fluorene imine (meth) acrylate, and the like ) Acrylic acid esters; (meth) acrylic acid esters containing hydrocarbon groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; (meth) acrylic acid (Meth) acrylates such as glycidyl (meth) acrylates and the like containing glycidyl groups.

The acrylic resin may be a resin obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, methylene succinic acid, vinyl acetate, acrylonitrile, styrene, and N-methyl methacrylamide.

The monomer constituting the acrylic resin may be only one kind, or two or more kinds.

In addition, in the present specification, "(meth) acrylic acid" includes both "acrylic acid" and "methacrylic acid", and "(meth) acrylic acid ester" includes "acrylic acid ester" and "methacrylic acid" "Ester".

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

The content of the acrylic resin in the solid content of the adhesive composition is preferably 50% by mass or more. Thereby, when the adhesive layer is used in a batch hardening process when the resin sealing of a semiconductor wafer is used, the adhesive layer has better properties. The reason is that in the aforementioned process, the wafer is wire-bonded before the semiconductor wafer is resin-sealed, but a certain degree of hardness can be ensured when the adhesive layer before curing is exposed to high temperatures, and this can be achieved here. Wire bonding is performed. That is, if the content of the acrylic resin in the adhesive composition is large, the storage elasticity of the adhesive layer can be increased before the thermosetting. Therefore, even in a state where the adhesive layer is not hardened or semi-hardened, vibration and displacement of the wafer during wire bonding can be suppressed, and wire bonding can be performed stably.

The solid content of the adhesive composition is more preferably 50 to 85% by mass based on the content of the acrylic resin. When the content of the acrylic resin is within the aforementioned range, the ease of picking up of a semiconductor wafer is improved.

In the present invention, (a) the adhesive resin can be used alone in order to improve the peelability of the adhesive layer and to improve the pick-up property, or to suppress the occurrence of pores by making the adhesive layer closely adhere to the uneven surface of the adherend. Thermoplastic resins other than acrylic resins (hereinafter simply referred to as "thermoplastic resins"), Can be used with acrylic resin.

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

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

Examples of the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

The above-mentioned effects can be obtained by using the aforementioned thermoplastic resin. On the other hand, the hardness of the adhesive layer before curing is lowered when exposed to high temperatures. In an unhardened or semi-hardened state, the lead connection of the adhesive layer is suitable. There is a risk of reduction. Therefore, it is preferable to set the content of the acrylic resin of the adhesive composition after considering the aforementioned effects.

(Epoxy-based thermosetting resin (b))

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

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

Examples of the epoxy resin include known epoxy resins, and specific examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrides thereof, o-cresol novolac epoxy resins, and bicyclic epoxy resins. Pentadiene ring Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and more than two functional epoxy compounds.

The epoxy resin may be an epoxy resin having an unsaturated hydrocarbon group. Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by changing a part of the epoxy resin of the polyfunctional epoxy resin to a group containing an unsaturated hydrocarbon group. The aforementioned compound can be produced, for example, by an addition reaction of acrylic acid and an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which an unsaturated hydrocarbon group-containing group is directly bonded to an aromatic ring or the like constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include a vinyl group, a 2-propenyl group, a propenyl group, a methacryl group, an acryl group, and a methyl group. Acrylamino is preferably acrylamido.

Compared with epoxy resins without unsaturated hydrocarbon groups, the compatibility between epoxy resins with unsaturated hydrocarbon groups and acrylic resins is higher. Therefore, by using an adhesive composition containing an epoxy resin having an unsaturated hydrocarbon group, the packaging reliability of a semiconductor device can be improved.

In view of improving the pick-up property, the aforementioned epoxy resin preferably has a higher softening point or a higher glass transition temperature.

Although the number average molecular weight of the said epoxy resin is not specifically limited, From the viewpoint of hardenability of an adhesive layer, the strength after hardening, and heat resistance Seen, it is preferably 300 ~ 30,000, more preferably 400 ~ 10000, and even more preferably 500 ~ 3000.

The epoxy equivalent of the aforementioned epoxy resin is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.

The said epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The function of the aforementioned thermosetting agent is a curing agent for epoxy resin hardening.

Examples of the thermosetting agent include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acidic anhydride group, and the phenolic hydroxyl group, an amine group, and an acidic anhydride group are preferred, and more preferably Phenolic hydroxyl group and amine group, particularly preferably phenolic hydroxyl group.

Examples of the phenol-based hardener (hardener having a phenolic hydroxyl group) among the thermal hardeners include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins. .

Examples of the amine-based hardener (hardener having an amine group) among the thermohardeners include DICY (dicyandiamide) and the like.

The said thermosetting agent may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent having an unsaturated hydrocarbon group include compounds obtained by substituting a part of hydroxyl groups of a phenol resin with a group containing an unsaturated hydrocarbon group, and compounds obtained by directly bonding an aromatic ring group with an unsaturated ring containing a phenol resin 组合 等。 And other. The unsaturated hydrocarbon group in the thermosetting agent is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

In view of improving the easy pick-up property, the aforementioned thermosetting agent is preferably a softening point or a high glass transition temperature.

The number average molecular weight of the aforementioned thermosetting agent is preferably 300 to 30,000, more preferably 400 to 10,000, and even more preferably 500 to 3,000.

The said thermosetting agent may be used individually by 1 type, and may use 2 or more types together.

The content of the thermosetting agent in the adhesive composition is 100 parts by mass with respect to the content of the epoxy resin, preferably 0.1 to 500 parts by mass, and more preferably 1 to 200 parts by mass. If the content of the thermosetting agent is too small, adhesiveness cannot be obtained due to insufficient hardening. If the content of the thermosetting agent is excessive, the moisture absorption rate of the adhesive layer increases, which reduces the reliability of the package.

The content of the epoxy-based thermosetting resin (b) of the adhesive composition (the total content of the epoxy resin and the thermosetting agent) is preferably 1 to 100 parts by mass relative to 100 parts by mass of the adhesive resin (a). It is more preferably 1.5 to 75 parts by mass, and even more preferably 2 to 60 parts by mass. Since the content of the epoxy-based thermosetting resin (b) is within the aforementioned range, the hardness of the adhesive layer before curing tends to be maintained, and the lead bonding suitability of the adhesive layer in an uncured or semi-cured state is improved. Moreover, the ease of picking up a semiconductor wafer is improved.

(Dye (s))

The dye (s) is described previously.

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

In order to improve various physical properties of the adhesive layer, the adhesive layer may be formed by using an adhesive composition which contains an adhesive resin (a), an epoxy-based thermosetting resin (b), and a dye (s). It also contains components other than the aforementioned components as needed.

Examples of other components contained in the adhesive composition include inorganic fillers (c), hardening accelerators (d), coupling agents (e), crosslinking agents (f), and epoxy-based thermosetting resins (b). Other thermosetting resins (g), general additives (h), etc.

(Inorganic filler (c))

The adhesive composition further contains an inorganic filler (c) to easily adjust its thermal expansion coefficient, and optimizes the thermal expansion coefficient of the cured adhesive layer for semiconductor wafers, metals, or organic substrates, thereby improving packaging. reliability.

In addition, the adhesive composition further reduces the moisture absorption of the adhesive layer after curing by further containing the inorganic filler (c).

As a preferable inorganic filler (c), there can be exemplified: silicon dioxide, Powders of alumina, talc, calcium carbonate, titanium white, iron white, silicon carbide, boron nitride, etc .; beads obtained by spheroidizing the aforementioned silica; etc .; surface modifiers such as the aforementioned silica; Single crystal fibers such as silicon; glass fibers.

Among them, the inorganic filler (c) is preferably a silica filler, an alumina filler, or a surface modification of these 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 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) can be exemplified by tertiary amines such as triethylene glycol, benzyl dimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminemethyl) phenol; Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazoles such as imidazole (imidazoles in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one hydrogen atom is replaced by an organic group) Phosphine); tetraphenylboron tetraphenylphosphine, tetraphenylboron triphenylphosphine and other tetraphenylboron salts.

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

When the hardening accelerator (d) is used, the content of the hardening accelerator (d) in the adhesive composition is 100 parts by mass with respect to the content of the epoxy-based thermosetting resin (b), and preferably 0.01 to 10 parts by mass. More preferably, it is 0.1 to 1 part by mass. By setting the content of the hardening accelerator (d) to the aforementioned 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 severe reflow conditions. Sex. If the content of the hardening accelerator (d) is too small, the effect obtained by using the hardening accelerator (d) cannot be fully obtained. If the content of the hardening accelerator (d) is excessive, the highly polar hardening accelerator (d) Under high-temperature and high-humidity conditions, the adhesive layer moves to the adhesion interface side of the adherend and segregates, which reduces the reliability of the package.

(Coupling agent (e))

The coupling agent (e) has a functional group that reacts with an inorganic compound and a functional group that reacts with an organic functional group. By using the coupling agent (e), the adhesiveness and adhesion of the adhesive layer to the adherend can be made. improve. In addition, by using the coupling agent (e), the cured product obtained by curing the adhesive layer can improve water resistance without impairing heat resistance.

The coupling agent (e) is preferably a compound having a functional group that reacts with a functional group such as an adhesive resin (a), an epoxy-based thermosetting resin (b), and the like, and is preferably a silane coupling agent.

Preferred examples of the aforementioned silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyl Trimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureido Propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyl Trimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, etc.

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) in the adhesive composition is 100 parts by mass based on the total content of the adhesive resin (a) and the epoxy-based thermosetting resin (b), and is preferably 0.03. 20 mass parts, more preferably 0.05 to 10 mass parts, and even more preferably 0.1 to 5 mass parts. If the content of the coupling agent (e) is too small, the aforementioned effects 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 aforementioned acrylic resin having a functional group capable of bonding to another compound such as an isocyanate group is used as the binder resin (a), a cross-linking agent (f) can be used to bond and crosslink the functional group with another compound. . By using the cross-linking agent (f), the initial adhesive force and cohesive force of the adhesive layer can be adjusted.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds and organic polyimide compounds.

Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and terpolymers, isocyanurates, and adducts of these compounds (with ethylene glycol). Alcohols, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil and other low-molecular active hydrogen-containing compounds (such as trimethylolpropane-added xylene diisocyanate, etc.), or organic polyisocyanate compounds and A terminal isocyanate urethane prepolymer obtained by reacting a polyol compound.

Specific examples of the organic polyisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene 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, and the addition of toluene diisocyanate or hexamethylene diisocyanate to all or part of hydrocarbon groups such as trimethylolpropane Compounds, lysine diisocyanate, etc.

Examples of the organic polyimide compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamidine), trimethylolpropane-tri-β-aziridinepropionic acid Esters, tetramethylolmethane-tri-β-aziridinylpropionate, N, N'-toluene-2,4-bis (1-aziridinecarboxamide) triethyl melamine, and the like.

When an isocyanate-based crosslinking agent is used as the crosslinking agent (f), the acrylic resin of the binder resin (a) is preferably a polymer containing a hydroxyl group. 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) and the acrylic resin.

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

(Other thermosetting resins (g))

The other thermosetting resin (g) may be any other epoxy resin than the epoxy resin in the epoxy-based thermosetting resin (b), and examples thereof include thermosetting polyimide resin, polyurethane resin, unsaturated polyester resin, and polysilicon. Oxygen resin and so on.

(General additive (h))

Examples of the general additive (h) include known plasticizers, antistatic agents, antioxidants, pigments, dyes, and getters.

(Solvent)

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

The solvent contained in the adhesive composition is not particularly limited, but examples of preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (2-methylpropane-1-ol ), Alcohols such as 1-butanol; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone; ethers such as tetrahydrofuran; amines such as dimethylformamide, N-methylpyrrolidone (compounds having amine bonds) .

The solvent contained in the adhesive composition may be only one kind, or two or more kinds.

Considering that the components used in the adhesive composition are uniformly mixed, the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like.

The adhesive composition is obtained by blending the dye (s) and the constituents of the adhesive layer other than the dye (s).

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

There is no particular limitation on the method of mixing the components during preparation, and a known method such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, or a method of applying ultrasonic mixing can be appropriately selected.

The temperature and time for adding and mixing the components are not particularly limited as long as the components are not deteriorated, as long as they are appropriately adjusted, the temperature is preferably 15 to 30 ° C.

When a solvent is used, the solvent can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance, or by not diluting any formulation component other than the solvent in advance, and mixing the solvent with the formulation component. use.

The adhesive layer can be formed in the same manner as in the case of forming the adhesive layer on the support substrate using the adhesive composition. However, when using the aforementioned adhesive substrate, it is often difficult to directly apply the adhesive composition to the adhesive layer. Therefore, for example, it is preferable to apply an adhesive composition on the surface of the release layer of the release material and dry to form an adhesive layer, and then attach the adhesive layer to the surface of the adhesive layer to remove the release material, etc., and then form it separately. A method in which the adhesive is adhered to the surface of the adhesive layer.

[Example]

Hereinafter, the present invention will be described in more detail based on specific examples. However, the present invention is not limited to the embodiments shown below.

<Manufacture of dicing die-bonding sheet>

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

(Manufacture of adhesive composition)

Each component was mix | blended in the quantity shown in Table 1, and it diluted with methyl ethyl ketone, and obtained the adhesive composition.

The abbreviations of the components in Table 1 have the following meanings.

‧Binder Resin (a)

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

‧Epoxy Thermosetting Resin (b)

(b) -11: Cresol novolac type epoxy resin with acrylamide ("CNA-147" manufactured by Nippon Kayaku Co., Ltd.)

(b) -21: Aralkylphenol resin ("MILEX XLC-4L" manufactured by Mitsui Chemicals)

‧Filling material (c)

(c) -1: Methacrylfluorene-based modified filler ("SO-C2" manufactured by ADMATECHS Corporation, with an average particle diameter of 0.5 µm, and 3-methylpropanoyloxypropyltrimethoxysilane of silicon dioxide Treatment)

‧Coupling agent (e)

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

‧Crosslinking agent (f)

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

‧Dye (s)

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

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

(Manufacture of dicing die-bonding sheet)

The adhesive-treated adhesive composition obtained above was coated on the peeling-treated surface of the release sheet on which one side of a polyethylene terephthalate film was peeled, and dried at 120 ° C. for 3 minutes to form a thickness of 5 μm or 20 μm adhesive layer. Further, the same release sheet as described above was bonded to the adhesive layer to produce two kinds of 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 20 μm of the adhesive layer in the aforementioned non-carrier film was used to peel off one of the release sheets, and the aforementioned adhesive layer was transferred to a dicing tape ("G-562" manufactured by LINTEC) '') To obtain a dicing die-bonding sheet. The base material of the dicing tape is white and the adhesive layer is colorless.

<Evaluation of dicing die-bonding sheet>

The obtained dicing die-bonding sheet was evaluated for the visual confirmation of the adhesive layer and the reliability of the semiconductor package by the following methods.

(Color difference (△ E) between the substrate and the adhesive layer)

Using a spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by SHIMADZU), the dicing tape ("G-562" manufactured by Lindec) was measured, and The light transmittance of the adhesive layer having a thickness of 5 μm obtained previously. 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 a 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 JISZ8781-4: 2013, and the color difference was calculated according to the aforementioned formula (I). (△ E). The results are shown in Table 1. Table 1 also shows L ^* , a ^* , and b ^{* of the} adhesive layer. In addition, L ^* of the dicing tape was 46, a ^* was 1.6, and b ^* was -2.9.

(Visual confirmation of adhesive layer)

Using an adhesive tape bonding machine ("Adwill RAD2500" manufactured by Lindec Corporation), the dicing die-bonding sheet having a thickness of 20 μm in the dicing die-bonding sheet of Examples and Comparative Examples was affixed through the adhesive layer. Attached to a polished surface of a dry-polished silicon wafer (150 mm in diameter and 75 μm thick), the silicon wafer was fixed to a ring frame for wafer cutting. Next, a dicing apparatus ("DFD651" manufactured by DISCO Corporation) was used to cut the silicon wafer into a size of 8 mm x 8 mm to obtain a wafer. In this cutting, 20 μm was cut into the substrate from the surface.

The aforementioned wafer to which the dicing die-bonding sheet is attached and the adhesive layer of the dicing die-bonding sheet are picked up from the substrate together. Next, a circuit pattern was formed on a copper foil (thickness: 18 μm) using a copper foil laminated laminate ("CCL-HL830" manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the circuit pattern was formed on the circuit pattern. Laminate a substrate ("LN001E-001 PCB (Au) AUS303" manufactured by Chino Giken) with solder resist ("PSR-4000 AUS303" manufactured by Sun Ink Co., Ltd.) at 120 ° C, 2.45N (250gf), 0.5 second Under the conditions, the aforementioned wafer with an adhesive layer is crimped onto the substrate via the adhesive layer. In addition, using the dicing die-bonding sheet having an adhesive layer thickness of 5 μm in the dicing die-bonding sheet obtained as described above, after obtaining a wafer in the same order as above, the wafer and the dicing die-bond are picked up from the base material together The adhesive layer is further crimped to the wafer which has been crimped to the substrate through the adhesive layer. In this process, visually observe the color of the adhesive layer seen between the ring frame and the wafer, and the color of the pickup portion of the wafer with the adhesive layer, and confirm whether these colors can be clearly identified by visual inspection. 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 they can be clearly identified by visual inspection, and "No" indicates that they cannot be clearly identified by visual inspection.

(Reliability of semiconductor package)

The laminate of the substrate and the wafer with the adhesive layer prepared at the time of the visual confirmation of the adhesive layer was heated at 175 ° C for one hour using an oven. Next, the laminate was taken out from the oven and cooled to normal 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) were used to seal the thickness. The laminate was sealed so as to have a thickness of 400 μm, and the mold resin was cured by heating at 175 ° C. for 5 hours. Next, the sealed laminate was affixed to a dicing tape ("Adwill D-510T" manufactured by Lindec) and cut to a size of 8 mm x 8 mm using a cutting device ("DFD651" manufactured by DISCO). Obtain a semiconductor package for evaluating reliability.

At 85 ° C and 60% relative humidity, the semiconductor package obtained above was left for 168 hours to absorb moisture, and then a reflow furnace ("WL-15-20DNX type" manufactured by Sagami Technology Co., Ltd.) Under the condition that the maximum heating temperature is 260 ° C and the heating time is one minute, IR reflow is performed 3 times.

Next, for the semiconductor package that was subjected to IR reflow, the joints of the substrate and the semiconductor wafer were observed from a cross section for floating and peeling, and peeling of 0.5 mm or more at the joints was judged as peeling. For 25 semiconductor packages, Count the number of unpackaged semiconductor packages. In addition, for the semiconductor package subjected to IR reflow, a scanning type ultrasonic flaw detection device ("Hye-Focus" manufactured by Hitachi Construction Machinery Fine Tech Co., Ltd.) was used to confirm whether or not a package crack occurred. The results are shown in Table 1. In Table 1, "No" indicates that no packaging crack occurred, and "Yes" indicates that a packaging crack occurred.

As a result, it was found that the adhesive layer of the dicing die-bonding sheet of Examples 1 to 6 contained a dye at a content of 0.1 to 8.3% by mass, so that ΔE was within a specific range, and the visual confirmation of the adhesive layer was excellent. The reliability of semiconductor packages is also improved.

On the other hand, since the adhesive layer of the dicing die-bonding sheet of Comparative Example 1 does not contain a dye, ΔE is outside a specific range, and the visual confirmation of the adhesive layer is not good.

In addition, even if the adhesive layer of the dicing die-bonding sheet of Comparative Example 2 contained a dye, ΔE was outside a specific range, and the visual confirmation of the adhesive layer was not good. In addition, since the content of the dye in the adhesive layer is too large, a large amount of peeling is observed at the joint portion between the substrate and the semiconductor wafer of the obtained semiconductor package, and package cracks are also generated, resulting in low reliability.

[Industrial availability]

The present invention can be used for manufacturing semiconductor wafers and the like.

Claims (3)

A dicing die-bonding sheet is provided on a substrate with an adhesive layer containing a dye; 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 b ^{* The} color difference in the color system is 30 ~ 53. The dicing die-bonding sheet according to claim 1, wherein the dye is a bisazo dye. The dicing die-bonding sheet according to claim 1 or 2, wherein the structure of the aforementioned dye does not include metal atoms or metal ions.