TWI770371B - Die bonding film, dicing die bonding sheet, and method for producing semiconductor chip - Google Patents

Abstract

A die bonding film including a first layer and a second layer provided on the first layer, wherein the first layer has a property that the initial detection temperature of the melt viscosity is 75℃ or less; the second layer has adhesiveness and energy ray curability; and the second layer has a property that the adhesive strength between a cured product having the width of 25mm and a silicon mirror wafer is 6N/25 mm or more, in a test laminate in which the cured product is attached to the silicon mirror wafer prepared by attaching a test piece which is the second layer having a thickness of 10μm and a width larger than 25mm to the silicon mirror wafer, cutting the test piece attached the silicon mirror wafer so as to have a width of 25mm, immersing the test piece after cutting in pure water together with the silicon mirror wafer for 2 hours and then curing the test piece after immersing with energy ray to obtain the cure product.

Description

Die bonding film, dicing die bonding sheet, and manufacturing method of semiconductor wafer

The present invention relates to a method for producing a die-bonding film, a dicing die-bonding sheet, and a semiconductor wafer. In this case, priority is claimed based on Japanese Patent Application No. 2018-057007 filed in Japan on March 23, 2018, the content of which is incorporated herein by reference.

In a semiconductor wafer, the circuit formation surface of a board|substrate is die-bonded normally via the die-bonding film attached to the inner surface. Then, if necessary, one or more semiconductor wafers are further laminated on this semiconductor wafer, and after wire bonding is performed, all of the obtained semiconductor wafers are sealed with resin to produce a semiconductor package. Thereafter, a target semiconductor device is fabricated using this semiconductor package.

The semiconductor wafer having the die-bonding film on the backside is produced by dividing (cutting) the semiconductor wafer having the die-bonding film on the backside together with the die-bonding film, for example. As a method of dividing such a semiconductor wafer into semiconductor wafers, for example, a method of dicing the semiconductor wafer together with the die-bonding film using a dicing blade is widely used. In this case, the die-bonding thin film layer before division (cutting) is integrated with a dicing sheet for fixing a semiconductor wafer at the time of dicing, and is used as a dicing die-bonding sheet. After the dicing is completed, the semiconductor wafer having the die-bonding film on the back surface (semiconductor wafer with the die-bonding film) is peeled off and picked up from the dicing sheet.

On the other hand, as a die-bonding film, for example, it has been disclosed that the elastic modulus G at 120° C. is 30,000 Pa or less (refer to Patent Document 1). According to Patent Document 1, the use of this die-bonding film can suppress the occurrence of voids (voids) at the interface of the die-bonding film on the semiconductor wafer side or the interface on the substrate side. Further, a die-bonding thin film composed of two layers of a wiring buried layer and an insulating layer laminated thereon has been disclosed (see Patent Document 2). According to Patent Document 2, this die-bonding film is suitable for the manufacture of a semiconductor package in which a wafer is three-dimensionally laminated. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-77855 [Patent Document 2] Japanese Patent Laid-Open No. 2007-53240

[Summary of Invention] [Problems to be Solved by Invention]

The diced semiconductor wafer is separated and picked up from the dicing sheet with the die-bonding film on the back as described above, and is die-bonded on the circuit formation surface of the substrate through the die-bonding film. However, the adhesive force (adhesion force) between the die-bonding film and the semiconductor wafer is insufficient, so that part or all of the die-bonding film is peeled off from the semiconductor wafer and remains on the dicing sheet during pick-up, and the die-bonding film is removed from the die-bonding film. The transfer of the dicing wafer to the semiconductor wafer will be abnormal. In this specification, this abnormality is called "transfer failure".

Such transfer failure of the die-bonding film is particularly likely to occur when a semiconductor wafer is divided into small-sized semiconductor wafers by using a dicing blade. This is because running water (also referred to as "cutting water") and dicing are performed simultaneously at the contact position between the dicing blade and the semiconductor wafer. The smaller the size of the semiconductor wafer obtained by dicing, the greater the contact amount of water with respect to the surface area of one semiconductor wafer, and thus is particularly susceptible to the influence of water. Therefore, when the adhesive force (adhesion force) between the die-bonding film and the semiconductor wafer is insufficient, water tends to penetrate into the interface between the die-bonding film and the semiconductor wafer. Once immersed in water, the die-bonding film is likely to be peeled off from the semiconductor wafer, and the above-mentioned transfer failure is likely to occur.

On the other hand, the die-bonding film disclosed in Patent Document 1 can suppress the occurrence of voids (voids) at the interface on the semiconductor wafer side, but it is uncertain whether it can suppress the pickup when the size of the semiconductor wafer is small. The transfer of the die-bonding film is poor.

Generally, in order to suppress the transfer defect of the die-bonding film, physical properties such as increasing the adhesive force of the die-bonding film can be improved. However, the die-bonding film is used for die-bonding semiconductor wafers on the circuit formation surface of the substrate. If the physical properties of the die-bonding film are improved to help suppress transfer defects, such as suppressing the occurrence of gaps between the substrate surface and the die-bonding film during die-bonding, the so-called die-bonding film-coated substrate surface will be reduced. the embeddedness of the substrate.

On the other hand, the die-bonding thin film disclosed in Patent Document 2 has a two-layer structure of a wiring embedding layer and an insulating layer, and teaches that the embedding property of the substrate is good. However, when the size of the semiconductor wafer is small, it is uncertain whether the insulating layer of the die-bonding film can suppress the transfer defect of the die-bonding film at the time of pick-up.

The present invention is to provide a die-bonding film capable of suppressing transfer defects to the semiconductor wafer when picking up a semiconductor wafer with a small size, and can be well embedded in a substrate during die-bonding, and a dicing die having the die-bonding film A bonding sheet and a method of manufacturing a semiconductor wafer using the dicing die bonding sheet are intended. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a die-bonding film comprising a first layer and a second layer on the first layer, wherein the first layer has a melt viscosity at an initial detection temperature of 75°C or lower, and the first layer has a melt viscosity of 75°C or lower. The two layers have adhesiveness and energy ray curability, and the second layer with a thickness of 10 μm and a width of more than 25 mm is used as a test piece, the test piece is attached to a silicon mirror wafer, and the test piece is cut. The test piece has a width of 25 mm, and the cut test piece and the mirror-surface silicon wafer are immersed in pure water for 2 hours. In the case of the laminated body for the test of the mirror-surface silicon wafer, the adhesive force between the cured product with a width of 25mm and the mirror-surface silicon wafer is 6N/25mm or more. Furthermore, the present invention provides a dicing die-bonding sheet comprising a support sheet and the die-bonding film on the support sheet, wherein the first layer in the die-bonding film is disposed on the support sheet side.

Furthermore, the present invention provides a method for manufacturing a semiconductor wafer, comprising producing a laminate (1-1) in which the semiconductor wafer is attached to the second layer and the dicing sheet is attached to the first layer in the die bonding film, Or in the aforementioned dicing die-bonding sheet, the step of attaching the laminate (1-2) of the semiconductor wafer to the second layer in the die-bonding film; by using a dicing blade, the aforementioned laminate (1-1) ) or the semiconductor wafer in the laminate (1-2) is cut together with the die-bonding film to produce a laminate having the cut first layer, the cut second layer, and the semiconductor wafer The process of the body (2): by curing the second layer after cutting in the layered body (2) with energy rays, a cured product is formed, and the first layer after cutting, the cured product, and the semiconductor wafer are produced. The step of the layered body (3); the step of separating and picking up the semiconductor wafer having the cut first layer and the cured product in the layered body (3) from the dicing sheet or the support sheet.

That is, the present invention includes the following aspects. [1] A die-bonding film comprising a first layer and a second layer on the first layer, Among them, the first layer has the characteristic that the initial detection temperature of the melt viscosity is 75°C or lower, The second layer has adhesiveness and energy ray curability, and The aforementioned die-bonding films have the following characteristics: The second layer with a thickness of 10 μm and a width of more than 25 mm is used as a test piece, the test piece is attached to a mirror-surface silicon wafer, the test piece is cut into a width of 25mm, and the cut test piece and the mirror-surface silicon wafer are cut. The wafers were immersed together in pure water for 2 hours, and the immersed test piece was energy ray-hardened to form a hardened product. When producing the test laminate in which the hardened product was attached to the mirror-surface silicon wafer, the width of the 25 mm The adhesive force between the hardened object and the aforementioned mirror-surface silicon wafer is 6N/25mm or more. [2] A dicing die-bonding sheet, comprising a support sheet and the die-bonding film as described in the above [1] on the aforementioned support sheet, The first layer in the die-bonding thin film is disposed on the support sheet side. [3] A method for manufacturing a semiconductor wafer, comprising: In the die-bonding film as described in the above [1], a semiconductor wafer is attached to the second layer, and a dicing sheet is attached to the first layer (1-1), or the above-mentioned [2] In the dicing die-bonding sheet according to the description, a laminate (1-2) in which the second layer of the die-bonding film is attached to a semiconductor wafer; The semiconductor wafer in the laminate (1-1) or the laminate (1-2) is cut together with the die-bonding film via a dicing blade to produce the first layer after cutting, the cutting The cut-off second layer and the semiconductor wafer laminate (2) of the cut-off semiconductor wafer; A layered body (3) having the first layer after cutting, the cured product, and the semiconductor wafer is produced by curing the second layer of the layered body (2) with energy rays after being cut to form a cured product; In the said laminated body (3), the said semiconductor wafer which has the said 1st layer after cutting|disconnection and the said hardened|cured material is separated and picked up from the said dicing sheet or the said support sheet. [Inventive effect]

According to the present invention, it is possible to provide a die-bonding film capable of suppressing poor transfer of a semiconductor wafer having a small size to a semiconductor wafer at the time of pick-up, and capable of being well embedded in a substrate at the time of die-bonding, and a dicing die having the die-bonding film. A bonding sheet, and a method of manufacturing a semiconductor wafer using the dicing die bonding sheet.

[For the form of implementing the invention]

◇Die-bonding film The die-bonding film according to an embodiment of the present invention comprises a first layer and a second layer on the first layer, wherein the first layer has an initial detection temperature of melt viscosity (this specification abbreviated as “T ₀ ”) is the characteristic below 75°C, the second layer has adhesiveness and energy ray curability, and has the following characteristics: the second layer with a thickness of 10 μm and a width of more than 25 mm is used as a test piece , the test piece was attached to the mirror-surface silicon wafer, the test piece was cut into a width of 25 mm, and the cut-off test piece and the mirror-surface silicon wafer were immersed in pure water for 2 hours to make the test after immersion. The sheet energy ray is hardened to form a hardened product. When the above-mentioned hardened product is attached to the above-mentioned mirror-surface silicon wafer for a test laminate, the adhesive force between the above-mentioned hardened product with a width of 25 mm and the above-mentioned mirror-surface silicon wafer (in this specification) abbreviated as "adhesion after dipping") is 6N/25mm or more. In addition, the present invention also includes a layer formed of the same material as the material for forming the second layer having the above-mentioned characteristics as a die-bonding thin film of the second layer.

In the above-mentioned die-bonding film, the first layer is used for die-bonding with respect to the substrate. On the other hand, the second layer is attached to the semiconductor wafer, hardened by irradiation with energy rays, and then picked up together with the semiconductor wafer. The attachment surface of the second layer of the semiconductor wafer is the surface on the opposite side of the circuit side of the semiconductor wafer (referred to as "back surface" in this specification).

In this specification, "energy ray" means what has energy quanta among electromagnetic waves or charged particle rays, and examples thereof include ultraviolet rays, radiation rays, electron rays, and the like. The ultraviolet rays can be irradiated with, for example, a high-pressure mercury lamp, a fusion lamp, a xeno lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated by an electron beam accelerator or the like. In this specification, "energy-beam curability" means the property of hardening by irradiation with energy rays, and "non-energy-beam hardenability" means the property of not hardening even when irradiated with energy rays.

In the above-mentioned die-bonding film, the first layer has adhesiveness. Therefore, since the initial detection temperature (T ₀ ) of the melt viscosity of the first layer is 75° C. or lower, the occurrence of a gap between the surface of the substrate and the first layer during die bonding is suppressed, and the first layer covers the substrate satisfactorily. On the surface, the first layer can be well embedded in the substrate.

On the other hand, in the above-mentioned die-bonding film, the second layer has adhesiveness and energy ray curability. Therefore, since the aforementioned adhesive force (adhesion force after immersion) measured with the test piece of the second layer was 6 N/25 mm or more, when a semiconductor wafer with a small size was picked up, part or all of the cured product of the second layer did not release from the semiconductor. The wafer is peeled off, and the cured product of the second layer can suppress the transfer defect to the semiconductor wafer, and has good transferability.

Therefore, the first layer and the second layer can maintain these laminated structures stably before and after the energy ray curing of the second layer. Therefore, the above-mentioned die-bonding film has both good transferability and good substrate embedding properties to a small-sized semiconductor wafer.

In this specification, the first layer is not in a laminated state with other layers, but exists alone, and such a first layer is referred to as a "first film".

Similarly, the second layer is not in a laminated state with other layers, but exists alone, and such a second layer is referred to as a "second film".

◎The first layer (the first film)

The said 1st layer (1st film) has adhesiveness as mentioned above.

Furthermore, the first layer may have curability (hardenability), or may not have curability (non-hardenability), and in the case of curability, for example, it may have one of thermosetting properties and energy ray hardening properties. It may have both thermosetting properties and energy ray hardening properties at the same time.

Both the non-curable first layer and the non-curable first layer with curability can be attached to various covering bodies by light pressure.

Moreover, the 1st layer can be attached to various covering bodies by softening it by heating, irrespective of whether it is hardened or not.

The first layer without curability and the cured product of the first layer with curability maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

T ₀ of the first layer is 75°C or lower, preferably 73°C or lower, more preferably 71°C or lower, more preferably 69°C or lower, for example, any of 66°C or lower and 62°C or lower. On the other hand, T ₀ of the first layer may be 68° C. or lower, or 59° C. or lower.

When T ₀ is equal to or less than the aforementioned upper limit value, the substrate embedding property of the first layer becomes higher.

The lower limit value of T ₀ in the first layer is not particularly limited.

The T ₀ of the first layer is preferably 50° C. or higher from the viewpoint of improving the handleability of the die-bonding thin film including the first layer.

T ₀ of the first layer can be set within the range of any combination of the above-mentioned preferable lower limit value and upper limit value, and can be adjusted appropriately. For example, T ₀ is preferably 50-75°C, more preferably 50-73°C, still more preferably 50-71°C, particularly preferably 50-69°C, for example, either 50-66°C and 50-62°C Can. On the other hand, T ₀ may be 50 to 68°C, or 50 to 59°C.

However, these are only examples of T ₀ for layer 1.

In the present embodiment, T ₀ of the first layer can be measured, for example, by the following method. That is, using a capillary rheometer, the first thin film (the first layer that exists alone) to be measured is set as, for example, a cylindrical test piece having a diameter of 10 mm and a height of 20 mm in its cylinder (capillary). , through a piston (piston) movable in the longitudinal direction of the cylinder (in other words, the central axis direction) along the inner wall of the cylinder, maintaining the first film (the aforementioned test piece) in the cylinder ) The state (loaded state) where a certain amount of force (for example, 5.10N (50kgf)) is applied, and the temperature of the first film (the aforementioned test piece) is simultaneously heated (for example, at a heating rate of 10°C/min, from 50°C to 120°C) . Then, from a hole (for example, a hole with a diameter of 0.5 mm and a height of 1.0 mm) provided at the front end of the column (the front end in the direction in which the force is applied to the first film (the test piece)), the first film is extruded to the outside of the column. (the test piece), that is, the temperature of the first film (the test piece) when the melt viscosity of the first film (the test piece) starts to be detected, the temperature of the first film (in other words, the first layer ) initial detection temperature T ₀ (°C). The size and shape of the first film to be measured can be appropriately adjusted in consideration of the size of a cylinder and the like.

In addition, in this specification, the "melt viscosity" means the melt viscosity measured by the above-mentioned method unless otherwise specified.

The first layer may be composed of one layer (single layer), or may be composed of two or more plural layers. When composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers There is no particular limitation.

In addition, in this specification, not limited to the case of the first layer, "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only a part of the layers may be the same. ”, and further, “a plurality of layers may be different from each other” means “at least one of the constituent material and thickness of each layer may be different from each other”.

The thickness of the first layer is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 30 μm, and more preferably 5 to 20 μm. When the thickness of the first layer is greater than or equal to the aforementioned lower limit value, the embedding property of the substrate of the first layer becomes higher. When the thickness of the first layer is equal to or less than the aforementioned upper limit value, the first layer (die-bonding film) can be more easily cut in the manufacturing process of the semiconductor wafer to be described later, and the cut pieces from the first layer can be further reduced. amount of occurrence. Here, the "thickness of the first layer" refers to the thickness of the entire first layer, for example, the thickness of the first layer composed of a plurality of layers refers to the total thickness of all the layers constituting the first layer.

The first layer (first thin film) can be formed from the first adhesive composition containing the constituent material. For example, the first layer can be formed on the target site by applying the first adhesive composition on the surface to be formed of the first layer, and drying it as necessary. The content ratio of components that do not vaporize at room temperature in the first adhesive composition is usually the same as the content ratio of the above-mentioned components in the first layer. In addition, in this specification, "normal temperature" means the temperature which is neither particularly cold nor particularly hot, that is, normal temperature, for example, the temperature of 15-25 degreeC etc. are mentioned.

The coating of the first adhesive composition can be performed by a known method, for example, the use of an air knife coater, a blade coater, or a bar coater can be used. , Gravure coater (gravure coater), roll coater (roll coater), roll knife coater (roll knife coater), curtain coater (curtain coater), die coater (die coater), knife A method of various coating machines such as knife coater, screen coater, meyer bar coater, kiss coater and the like.

The drying conditions of the first adhesive composition are not particularly limited, but when the first adhesive composition contains a solvent described later, it is preferable to heat-dry it. The solvent-containing first adhesive composition is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes. Hereinafter, the first adhesive composition will be described in detail.

>>First Adhesive Composition>> The type of the first adhesive composition is selected according to the properties of the first layer such as the presence or absence of curability of the first layer and, when the first layer is curable, whether or not it is thermosetting and energy ray curable. As a preferable 1st adhesive composition, the thermosetting 1st adhesive composition is mentioned. As a thermosetting 1st adhesive composition, the polymer component (a) and epoxy-type thermosetting resin (b) are mentioned, for example. Hereinafter, each component will be described.

(polymer component (a)) The polymer component (a) can be regarded as a component formed by a polymerization reaction of a polymerizable compound, and is intended to provide the first layer with film-forming properties, flexibility, etc., and to improve adhesion (sticking) to an object to be bonded such as a semiconductor wafer. ) polymer compounds. In addition, the polymer component (a) may be a component not corresponding to the epoxy resin (b1) and the thermosetting agent (b2) described later. That is, the polymer component (a) does not include components corresponding to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The first adhesive composition and the polymer component (a) contained in the first layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

Polymer component (a) such as acrylic resin, polyester, urethane resin, urethane acrylate resin, silicone resin, rubber resin, phenoxy Resins, thermosetting polyimides, etc. are preferably acrylic resins.

The aforementioned acrylic resin in the polymer component (a) is, for example, a known acrylic polymer. 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. When the weight average molecular weight of the acrylic resin is within such a range, it is easy to adjust the adhesive force between the first layer and the covering to a preferable range. On the other hand, when the weight average molecular weight of the acrylic resin is at least the aforementioned lower limit value, the shape stability (temporal stability during storage) of the first layer is improved. Moreover, when the weight average molecular weight of an acrylic resin is below the said upper limit, the embedding property of the board|substrate of a 1st layer becomes higher. In addition, in this specification, the "weight average molecular weight" is a polystyrene conversion value measured by gel permeation chromatography (GPC) unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, preferably -30 to 50°C. When the Tg of the acrylic resin is greater than or equal to the aforementioned lower limit value, the adhesive force between the first layer and the support sheet or dicing sheet described later is suppressed, and the semiconductor wafer having the first layer at the time of pickup becomes easier to support from the support sheet described later. sheet or cut sheet separation. Tg of an acrylic resin is below the said upper limit, and the adhesive force between a 1st layer and a 2nd layer improves.

Examples of the (meth)acrylates constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate ) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate Esters, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexadecyl (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate having a chain structure with 1 to 18 carbon atoms; Cycloalkyl (meth)acrylates such as (meth)isobornyl acrylate, dicyclopentyl (meth)acrylate, etc.; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate; (meth)imide acrylate; Glycidyl-containing (meth)acrylates such as (meth)glycidylacrylates; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxyl (meth)acrylate Hydroxyl-containing (meth)acrylates such as butyl ester, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Substituted amino group-containing (meth)acrylates such as N-methylaminoethyl (meth)acrylate and the like. Here, the "substituted amino group" refers to a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

In addition, in this specification, "(meth)acrylic acid" includes the concepts of both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic.

The acrylic resin may be, for example, other than the aforementioned (meth)acrylate, selected from (meth)acrylate, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N - One or two or more monomers such as methylol acrylamide are copolymerized.

The monomer constituting the acrylic resin may be only one type or two or more types, and in the case of two or more types, the combination and the ratio thereof can be arbitrarily selected. In one aspect, the aforementioned acrylic resin is an acrylic resin obtained by copolymerization of n-butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate, or n-butyl acrylate, ethyl acrylate An acrylic resin obtained by copolymerizing ester, acrylonitrile, and glycidyl methacrylate is preferable.

The acrylic resin may have functional groups such as vinyl groups, (meth)acryloyl groups, amine groups, carboxyl groups, and isocyanate groups, which can be bonded to other compounds, in addition to the aforementioned hydroxyl groups. These functional groups such as the hydroxyl group of the acrylic resin may be bonded via the crosslinking agent (f) and other compounds described later, or may not be directly bonded via the crosslinking agent (f) and other compounds described later. The acrylic resin tends to improve the reliability of the obtained package by using the first layer because the above-mentioned functional groups are bonded to other compounds.

In the present invention, as the polymer component (a), a thermoplastic resin other than the acrylic resin may be used alone without using the acrylic resin (it may simply be abbreviated as "thermoplastic resin" hereinafter), or an acrylic resin may be used in combination. By using the above-mentioned thermoplastic resin, the semiconductor wafer having the first layer can be more easily separated from the support sheet or the dicing sheet to be described later at the time of picking up, and the embedding property of the substrate of the first layer can be improved.

The weight-average molecular weight of the aforementioned thermoplastic resin is preferably 1,000-100,000, and preferably 3,000-80,000.

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

The aforementioned thermoplastic resins are, for example, polyester, polyurethane, phenolic resin, polybutene, polybutadiene, polystyrene, and the like.

Only one kind of the thermoplastic resin contained in the first adhesive composition and the first layer may be used, or two or more kinds thereof may be sufficient, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.

In the first adhesive composition, the ratio of the content of the polymer component (a) to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (a) in the first layer) ) is, regardless of the type of the polymer component (a), preferably 5 to 20 mass %, preferably 6 to 16 mass %, and more preferably 7 to 12 mass %.

In the first adhesive composition and the first layer, the ratio of the content of the acrylic resin to the total content (total mass) of the polymer component (a) is preferably 80 to 100 mass %, preferably 85 to 100 mass % Preferably, 90-100 mass % is more preferable, for example, 95-100 mass % may be sufficient.

(Epoxy-based thermosetting resin (b))

The epoxy-based thermosetting resin (b) consists of an epoxy resin (b1) and a thermosetting agent (b2).

Only one type of epoxy-based thermosetting resin (b) contained in the first adhesive composition and the first layer may be used, or two or more types, and in the case of two or more types, the combination and the ratio can be arbitrarily selected.

‧Epoxy resin (b1)

As the epoxy resin (b1), known ones can be mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resins, bicyclic epoxy resins can be mentioned. Bi-functional or higher epoxy compounds such as pentadiene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and phenylene structure-type epoxy resins.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package using the first layer is improved.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound which converted a part of the epoxy group of a polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction to an epoxy group. In addition, in this specification, unless otherwise specified, the "derivative" refers to a compound formed by substituting at least one group of the original compound with another group (substituent). Here, the term "group" refers not only to an atomic group in which a plurality of atoms are bonded, but also includes one atom.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which directly couple|bond the group which has an unsaturated hydrocarbon group, such as the aromatic ring which comprises an epoxy resin, are mentioned. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), (Meth)acryloyl group, (meth)acrylamido group, etc., preferably acryl group.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but from the viewpoint of the curability of the first layer and the strength and heat resistance of the cured product of the first layer, 300 to 30,000 is preferable, and 400 to 10,000 is preferable. Good, 500~3000 is very good.

In this specification, unless otherwise specified, the number average molecular weight is a polystyrene conversion value measured by colloid permeation chromatography (GPC).

The epoxy equivalent of the epoxy resin (b1) is preferably 100-1000 g/eq, and preferably 150-800 g/eq. In this specification, "epoxy equivalent" represents the number of grams (g/eq) of the epoxy compound containing 1 equivalent of epoxy group, and can be measured according to the method of JIS K 7236:2001.

Only one type of epoxy resin (b1) contained in the first adhesive composition and the first layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

In one aspect, the aforementioned epoxy resin (b1) is selected from the group consisting of bisphenol A type epoxy resin, polyfunctional aromatic type (triphenyl type) epoxy resin, bisphenol F type epoxy resin, and dicyclopentadiene At least one of the olefinic epoxy resins is preferred.

‧Thermosetting agent (b2)

The thermosetting agent (b2) acts as a curing agent for the epoxy resin (b1).

As a thermosetting agent (b2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. The aforementioned functional groups, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, oxyacid anhydride groups, etc., preferably phenolic hydroxyl groups, amino groups, or oxyacid anhydride groups, phenolic hydroxyl groups or amine groups base is better.

Among the phenolic hardeners having a phenolic hydroxyl group in the thermosetting agent (b2), for example, polyfunctional phenol resins, bisphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenols can be mentioned. resin, etc.

As an amine-type hardening agent which has an amine group in a thermosetting agent (b2), dicyandiamide (dicyandiamide, abbreviated as DICY) etc. are mentioned, for example.

The thermal hardener (b2) may also have an unsaturated hydrocarbon group.

The thermosetting agent (b2) having an unsaturated hydrocarbon group, for example, a compound formed by substituting a part of the hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, and the aromatic ring of the phenol resin is directly bonded to a compound having an unsaturated hydrocarbon group. compounds formed by bases, etc.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (b2) is the same as the aforementioned unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

When a phenolic hardener is used as the thermosetting agent (b2), the thermosetting agent (b2) is preferably one having a higher softening point or glass transition temperature from the viewpoint of making it easier to adjust the adhesive force of the die-bonding film.

Among the thermosetting agents (b2), for example, polyfunctional phenol resins, novolac-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl-type phenol resins and the like are preferably those having a number average molecular weight of 300 to 30,000, 400~10000 is better, 500~3000 is especially good.

In the thermosetting agent (b2), for example, the molecular weight of non-resin components such as bisphenol and dicyandiamide is not particularly limited, but, for example, it is preferably 60 to 500°C.

Only one type of thermosetting agent (b2) contained in the first adhesive composition and the first layer may be sufficient, or two or more types may be sufficient, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

In the thermosetting agent (b2), it can also be used as a phenol resin, for example, substitution of a carbon atom bonded to a phenolic hydroxyl group and an adjacent carbon atom (carbon atom constituting a benzene ring structure), a bonded alkyl group, etc. A group having a steric barrier in the vicinity of the aforementioned phenolic hydroxyl group (in this specification, it is abbreviated as "stereobarrier-type phenol resin"). Such a steric barrier-type phenolic resin is, for example, an o-cresol-type phenolic resin or the like.

In the first adhesive composition and the first layer, with respect to 100 parts by mass of the epoxy resin (b1), the content of the thermosetting agent (b2) is preferably 10 to 200 parts by mass, and preferably 15 to 160 parts by mass Preferably, 20 to 120 parts by mass is more preferred, and 25 to 80 parts by mass is particularly preferred. When the said content of a thermosetting agent (b2) is more than the said lower limit, hardening of a 1st layer becomes easier. When the said content of a thermosetting agent (b2) is below the said upper limit, the moisture absorption rate of a 1st layer reduces, and the reliability of the package using a 1st layer is improved more.

In the first adhesive composition and the first layer, with respect to 100 parts by mass of the content of the polymer component (a), the content of the epoxy-based thermosetting agent (b) (epoxy resin (b1) and thermosetting agent (b2) ) is preferably 400-1200 parts by mass, preferably 500-1100 parts by mass, more preferably 600-1000 parts by mass, for example, 600-900 parts by mass, and 800-1000 parts by mass Either. When the content of the epoxy-based thermosetting agent (b) is within such a range, it is easier to adjust the adhesive force between the first layer and a support sheet or a dicing sheet to be described later.

When the aforementioned steric-barrier-type phenol resin is used, the content ratio of the aforementioned steric-barrier-type phenol resin relative to the total content (total mass) of the thermosetting agent (b2) in the first adhesive composition and the first layer may be, for example, Any of 80 to 100 mass %, 85 to 100 mass %, 90 to 100 mass %, and 95 to 100 mass %. Therefore, the content ratio of the o-cresol-type phenolic resin may be 80 to 100 mass % and 85 to 100 mass % relative to the total content (total mass) of the thermosetting agent (b2) in the first adhesive composition and the first layer. %, 90-100 mass %, and any one of 95-100 mass %.

In order to improve various physical properties, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), the first layer may contain other components not corresponding to these as necessary. Other components contained in the first layer include, for example, curing accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), energy ray curable resin (g), photopolymerization Initiator (h), general additive (i), etc. Among these, preferable other components mentioned above include, for example, a hardening accelerator (c), a filler (d), a coupling agent (e), and a widely used additive (i).

(hardening accelerator (c)) The hardening accelerator (c) is a component for adjusting the hardening rate of the first adhesive composition. Preferred hardening accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine ethanol, and tris(dimethylaminomethyl)phenol. ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole (imidazoles in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (at least one hydrogen atom) A phosphine whose atom is substituted by an organic group); tetraphenyl borate salts of tetraphenyl boron tetraphenyl phosphonium, tetraphenyl boron triphenyl phosphonium, etc.; inclusion compounds of the aforementioned imidazoles as guest compounds, and the like.

The first adhesive composition and the hardening accelerator (c) contained in the first layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

When the curing accelerator (c) is used, in the first adhesive composition and the first layer, the content of the curing accelerator (c) is 0.01 to 0.01 parts by mass relative to 100 parts by mass of the epoxy-based thermosetting resin (b). 5 parts by mass is preferred, and 0.1 to 2 parts by mass is preferred. When the said content of the hardening accelerator (c) is more than the said lower limit, the effect by using the hardening accelerator (c) can be obtained more remarkably. If the content of the curing accelerator (c) is not more than the upper limit, for example, a highly polar curing accelerator (c) suppresses movement to the interface side with the coating in the first layer under high temperature and high humidity conditions The effect of segregation is increased, and the reliability of the package obtained by using the first layer is further improved.

In the above, in the inclusion compound in which the imidazoles are used as the guest compound, the imidazoles as the active ingredient are included via the host compound. Therefore, it is presumed that the reaction site of the imidazoles is not exposed or the degree of exposure is suppressed except during the reaction. As a result, when the above-mentioned inclusion compound is used as the curing accelerator (c), it is presumed that the storage stability of the first layer is stable because the progress of the reaction outside the target of the curing accelerator (c) is suppressed during the storage of the first layer. become higher.

The aforementioned inclusion compound includes, for example, imidazoles as a guest compound and a carboxylic acid as a host compound.

The aforementioned carboxylic acid as the host compound is preferably an aromatic carboxylic acid. The aforementioned aromatic carboxylic acid may be either a monocyclic aromatic carboxylic acid or a polycyclic aromatic carboxylic acid. The aforementioned aromatic carboxylic acid may be a carboxylic acid having only an aromatic hydrocarbon ring as a ring structure, a carboxylic acid having only an aromatic heterocycle as a ring structure, or a carboxylic acid having both an aromatic hydrocarbon ring and an aromatic heterocycle as the ring structure any of .

The aforementioned aromatic carboxylic acid is preferably an aromatic hydroxycarboxylic acid. The above-mentioned aromatic hydroxycarboxylic acid is not particularly limited as long as it is an aromatic carboxylic acid having both a hydroxyl group and a carboxyl group in one molecule, but is preferably a carboxylic acid having a hydroxyl group and a carboxyl group bond structure in an aromatic ring structure.

The aforementioned inclusion compound is preferable, for example, the aforementioned imidazoles are 2-phenyl-4-methyl-5-hydroxymethylimidazole (abbreviated as "2P4MHZ" in this specification), and the aforementioned carboxylic acid is 5-hydroxyl As the inclusion compound of isophthalic acid (abbreviated as "HIPA" in this specification), it is more preferable that two molecules of 2P4MHZ and one molecule of HIPA constitute one molecule of the inclusion compound.

When the inclusion compound is used, in the first adhesive composition and the first layer, the content ratio of the inclusion compound may be 80 to 100 mass % relative to the total content (total mass) of the hardening accelerator (c). , any of 85 to 100 mass %, 90 to 100 mass %, and 95 to 100 mass %. Therefore, in the first adhesive composition and the first layer, the content ratio of the inclusion compound composed of the above-mentioned 2P4MHZ and HIPA can be 80 to 100 mass relative to the total content (total mass) of the curing accelerator (c). %, any of 85 to 100 mass %, 90 to 100 mass %, and 95 to 100 mass %.

(filler (d)) Since the first layer contains the filler (d), its thermal expansion coefficient can be easily adjusted, and this thermal expansion coefficient is optimized for the object to which the first layer is attached, which further improves the reliability of the package obtained by using the first layer. Moreover, since a 1st layer contains a filler (d), the moisture absorption rate of the 1st layer after hardening can be lowered|hung, and heat radiation property can also be improved.

The filler (d) may be either an organic filler or an inorganic filler, but an inorganic filler is preferable. Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, boron nitride, etc.; spherical beads made of these inorganic fillers (beads); surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica or alumina.

The average particle size of the filler (d) is not particularly limited, but is preferably 1 to 1000 nm, preferably 5 to 800 nm, more preferably 10 to 600 nm, for example, any of 10 to 400 nm and 10 to 200 nm. On the other hand, the average particle diameter of the filler (d) may be 50 to 500 nm. When the average particle diameter of the filler (d) is within such a range, it becomes easier to adjust the thermal expansion coefficient, the moisture absorption rate, and the heat release properties. In addition, unless otherwise specified, the "average molecular weight" in this specification means the value of the particle size (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method.

Only one type of filler (d) contained in the first adhesive composition and the first layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

When the filler (d) is used, in the first adhesive composition, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent (that is, the filling of the first layer) The material (d) content) is preferably 5 to 40 mass %, preferably 10 to 35 mass %, and particularly preferably 15 to 30 mass %. When the content of the filler (d) is within such a range, it becomes easier to adjust the thermal expansion coefficient, the moisture absorption rate, and the heat release properties.

When the filler (d) having an average particle diameter of 1 to 1000 nm is used, in the first adhesive composition and the first layer, the average particle diameter with respect to the total content (total mass) of the filler (d) is The content ratio of the filler (d) of 1 to 1000 nm is preferably 80 to 100 mass %, preferably 85 to 100 mass %, more preferably 90 to 100 mass %, and may be, for example, 95 to 100 mass %.

(Couplant (e)) Since the first layer contains the coupling agent (e), the adhesion and adhesion to the coated body are improved. Moreover, since the 1st layer contains a coupling agent (e), the hardened|cured material loses heat resistance, and water resistance improves. The coupling agent (e) has a functional group reactive with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group reactive with the functional group of the polymer component (a), the epoxy-based thermosetting resin (b), and the like, and a silane coupling agent is preferred. Preferred above-mentioned silane coupling agents, for example, 3-glycidyl (glycidyl) oxy (oxy) propyl trimethoxy silane, 3-glycidyloxy propyl methyl diethoxy silane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Silane, 3-Methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3 -(2-Aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-urea ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) ) tetrasulfide (sulfide), methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazosilane, oligomeric or polymeric Organosiloxane etc. The oligomer-type or polymer-type organosiloxane can be regarded as an organosiloxane having an oligomer structure or a polymer structure formed by polymerizing a polymerizable compound.

Only one type of the coupling agent (e) contained in the first adhesive composition and the first layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and the ratio can be arbitrarily selected. In one aspect, the aforementioned coupling agent (e) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and epoxy, methyl At least one of the oligomer type silane coupling agent of methoxy group and methoxy group is preferable.

In the case of using the coupling agent (e), in the first adhesive composition and the first layer, the content of the coupling agent (e) relative to the content of the polymer component (a) and the epoxy-based thermosetting resin (b) The total content of 100 parts by mass is preferably 0.03 to 20 parts by mass, preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the above-mentioned content of the coupling agent (e) is more than the above-mentioned lower limit value, the dispersibility to the resin of the filler (d) is improved, the adhesiveness of the covering body of the first layer is improved, and the like can be obtained by using the coupling agent (e) more pronounced effect. When the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of outgas is suppressed more.

When an oligomer type or polymer type organosiloxane is used, in the first adhesive composition and the first layer, with respect to the total content (total mass) of the coupling agent (e), the aforementioned oligomer type Or the ratio of the content of the polymer-type organosiloxane may be any of 25 to 100 mass % and 40 to 100 mass %.

(Crosslinker (f)) When using functional groups such as vinyl groups, (meth)acryloyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc. which can be bonded to other compounds in the above-mentioned acrylic resins as the polymer component (a), The first adhesive composition and the first layer may also contain a crosslinking agent (f) for crosslinking by bonding the above-mentioned functional groups and other compounds. When the crosslinking agent (f) is used for crosslinking, the initial adhesion force and cohesion force of the first layer can be adjusted.

The crosslinking agent (f) includes, for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate type crosslinking agent (that is, a crosslinking agent having a metal chelate structure), an aziridine (aziridine) ) is a crosslinking agent (ie, a crosslinking agent having an aziridinyl group) and the like.

The aforementioned organic polyvalent isocyanate compounds include, for example, aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are simply referred to as "aromatic polyvalent isocyanate compounds, etc." ); trimers, isocyanurate esters, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate groups obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. of urethane prepolymers, etc. The aforementioned "adduct" means the aforementioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil and other reactants of compounds containing small molecules of active hydrogen. As an example of the said adduct, the xylene diisocyanate adduct of trimethylolpropane mentioned later, etc. are mentioned. In addition, "urethane prepolymer with terminal isocyanate group" means a prepolymer having an isocyanate group at the molecular terminal while having a urethane bond.

More specific examples of the organic polyvalent isocyanate compound include 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-toluene diisocyanate; 1,4-toluene diisocyanate ; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone ( isophorone) diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of the hydroxyl groups of polyalcohols such as trimethylolpropane, there are toluene Any one or two or more addition compounds of diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; lysine diisocyanate, and the like.

As the aforementioned organic polyvalent imide compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyimide), trimethylolpropane-tri-β- Aziridine propionate, tetramethylolmethane-tri-beta-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxyamide)triethylenemelamine ( melamine) etc.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinking structure can be easily introduced into the first layer through the reaction between the crosslinking agent (f) and the polymer component (a).

Only one type of the crosslinking agent (f) contained in the first adhesive composition and the first layer may be used, or two or more types may be used, and in the case of two or more types, the combination and the ratio thereof can be arbitrarily selected.

In the first adhesive composition and the first layer, the content of the crosslinking agent (f) is preferably 0 to 5 parts by mass, preferably 0 to 3 parts by mass, with respect to 100 parts by mass of the content of the polymer component (a). 0 to 1 part by mass is more preferable, and 0 part by mass, that is, the first adhesive composition and the first layer that do not contain the crosslinking agent (f) are particularly preferred. When the said content of a crosslinking agent (f) is below the said upper limit, the embedding property of the board|substrate of a 1st layer becomes higher.

(Energy beam curable resin (g)) Since the first layer contains the energy ray curable resin (g), the properties can be changed by irradiation with energy rays.

The energy ray curable resin (g) is obtained by polymerizing (hardening) an energy ray curable compound. As the energy ray curable compound, for example, a compound having at least one polymerizable double bond in the molecule is exemplified, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. , Neotaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, (Meth)acrylates having a chain aliphatic structure such as 1,6-hexanediol di(meth)acrylate; cyclic aliphatic structures such as dicyclopentyl di(meth)acrylate (meth)acrylate; polyalkylene glycol (meth)acrylate such as polyethylene glycol di (meth)acrylate; oligoester (meth)acrylate; urethane (meth)acrylic acid Ester oligomers; epoxy group-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itonic acid oligomers, and the like.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

Only one type of the energy ray-curable resin (g) contained in the first adhesive composition may be sufficient, or two or more types may be sufficient, and in the case of two or more types, the combination and the ratio can be arbitrarily selected. In one aspect, the above-mentioned energy ray curable resin (g) is selected from tricyclodecane dimethylol diacrylate and ε-caprolactone (caprolactone) modified para-(2-acryloxy) oxyethyl At least one type of trimeric isocyanate is preferred.

When the energy ray curable resin (g) is used, in the first adhesive composition, the content of the energy ray curable resin (g) is 1 to 95% by mass relative to the total mass of the first adhesive composition. 5-90 mass % is preferable, and 10-85 mass % is especially preferable.

(Photopolymerization initiator (h)) When the first adhesive composition contains the energy ray curable resin (g), in order to efficiently promote the polymerization reaction of the energy ray curable resin (g), a photopolymerization initiator (h) may be contained.

The photopolymerization initiator (h) in the first adhesive composition, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether , benzoin benzoic acid, benzoin benzoate methyl ester, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane- Acetophenone compounds such as 1-keto, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.; bis(2,4,6-trimethylbenzyl)benzene Phosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc.; benzylphenyl sulfide, tetramethylthiuram monosulfide Sulfur compounds such as compounds; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenone; azo compounds such as azobisisobutyronitrile; thioxanthone compounds; peroxy compounds; diketone compounds such as diacetyl; benzil; bibenzyl; diphenyl ketone; 2,4-diethylthioxanthone; ,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone Wait. Moreover, as a photoinitiator (h), photosensitizers, such as an amine, are mentioned, for example.

The photopolymerization initiator (h) contained in the first adhesive composition may be only one type or two or more types, and in the case of two or more types, the combination and the ratio can be arbitrarily selected.

In one aspect, the photopolymerization initiator (h) is preferably 2-benzyl-2-dimethylamino-1-(4-morpholino)-butanone-1.

When the photopolymerization initiator (h) is used, in the first adhesive composition and the first layer, the content of the photopolymerization initiator (h) relative to 100 parts by mass of the energy ray curable resin (g) content 0.1-20 mass parts is preferable, 1-10 mass parts is preferable, and 2-5 mass parts is especially preferable.

(General Additive (i))

The widely used additive (i) may be any known one, and can be arbitrarily selected depending on the purpose, and is not particularly limited. Preferred general additives (i) are, for example, plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), gattering agents, and the like.

The first adhesive composition and the general-purpose additive (i) contained in the first layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

The content of the first adhesive composition and the widely used additive (i) of the first layer is not particularly limited, and may be appropriately selected depending on the purpose.

(solvent)

It is preferable that the first adhesive composition further contains a solvent. The handleability of the solvent-containing first adhesive composition becomes favorable.

The aforementioned solvent is not particularly limited, and preferable ones include, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (also referred to as 2-methylpropan-1-ol), 1-butane Alcohols such as alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide, N-methylpyrrodidone (ie, compounds with an amide bond), etc.

The solvent contained in the first adhesive composition may be one type or two or more types, and in the case of two or more types, the combination and the ratio can be arbitrarily selected.

The solvent contained in the first adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the first adhesive composition can be mixed more uniformly.

A preferred example of the first adhesive composition includes a polymer component (a), an epoxy-based thermosetting resin (b), a curing accelerator (c), and a coupling agent (e), and other than these In addition, it is possible to further contain either or both of the filler (d) and the widely used additive (i).

>>Manufacturing method of 1st adhesive composition>> The first adhesive composition is obtained by blending the components constituting this. When each component is prepared, the order of addition is not particularly limited, and two or more components may be added at the same time. When a solvent is used, the solvent may be mixed with any preparation component other than the solvent, and the preparation component may be diluted beforehand for use, or the solvent may be mixed with these preparation components without prior dilution of any preparation component other than the solvent.

The method of mixing each component at the time of preparation is not limited, and can be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of adding ultrasonic mixing. The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounded component is not degraded, and can be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◎The second layer (the second film) The second layer (second film) has adhesiveness and energy ray curability as described above. The second layer may be more thermosetting (may be thermosetting) or may not have thermosetting (may be non-thermosetting). In particular, it is preferable that the second layer does not have thermosetting property but has energy ray hardening property.

Both the non-curable second layer and the non-curable second layer with curability can be lightly pressed and attached to various covering bodies. In addition, the second layer can be attached to various covering bodies regardless of whether it is hardened or not, by heating and softening it. The second layer without curability and the cured product of the second layer with curability can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The above-mentioned laminated body for the test having an adhesive force after immersion of 6 N/25 mm or more was produced as follows. That is, a second layer having a thickness of 10 μm and a width of more than 25 mm was prepared as a test piece. The second layer is prepared, for example, as a laminate with a release film, and by using this laminate, a laminate for testing can be more easily produced. In this case, the aforementioned release film can be removed at an appropriate timing.

The length of the test piece is not particularly limited as long as the peeling test described later can be performed stably, but, for example, it is preferably 15 cm or more and 30 cm or less.

Next, attach this sample to a mirrored silicon wafer. The aforementioned test piece is preferably attached to a mirror-surface silicon wafer in a state of being heated to 35 to 45°C. In addition, when the test piece is attached to the mirror-surface silicon wafer, the attachment speed and the attachment pressure are not particularly limited. For example, the sticking speed is preferably 5~20mm/s, and the sticking pressure is preferably 0.1~1.0MPa.

Then, on the exposed surface of the attached test piece (ie, the second layer after attaching the mirror-surface silicon wafer) (the surface on the opposite side of the mirror-surface silicon wafer side), a tape-shaped strong adhesive with a width of 25 mm is attached. adhesive tape.

Then, with respect to the test piece (2nd layer) after attaching this strong adhesive tape, the band-shaped notch of width 25mm was formed along the periphery of the strong adhesive tape. This mark was formed on the entire area of the test piece in the thickness direction. That is, the sample piece was cut into a strip shape having a width of 25 mm.

After that, the cut test piece and the mirror-surface silicon wafer (in other words, the mirror-surface silicon wafer having the cut test piece) were immersed in pure water at 23° C. for 2 hours. At this time, the mirror-surface silicon wafer having the test piece after cutting is placed in the pure water in a state in which all the test pieces and the mirror-surface silicon wafer after cutting are immersed in pure water. in water. The mirror-surface silicon wafer having the test piece after cutting is preferably immersed in pure water immediately after its production. In this way, the up-front adhesive force of the test laminate can be measured with higher accuracy. The mirror-surface silicon wafer with the test piece after cutting is preferably immersed in pure water in a dark place. In this way, the aforementioned adhesive force of the test laminate can be measured with higher accuracy.

The mirror-surface silicon wafer having the test piece after cutting was immersed in pure water for 2 hours, then taken out from the pure water, and when remaining water droplets adhered to the surface, the water droplets were removed. Then, the test piece (second layer) after being cut is irradiated with energy ray to harden the strip-shaped test piece with energy ray.

The irradiation conditions of the energy beam are not particularly limited as long as the test piece can be sufficiently cured by the energy beam. For example, it is preferable that the illuminance of the energy beam at the time of energy beam curing is 4 to 280 mW/cm ² . The light intensity of the energy ray at the time of energy ray curing is preferably 3 to 1000 mJ/cm ² .

According to the above, a laminated body for testing in which the mirror-surface silicon wafer is adhered to the hardened product of the test piece (the second layer) and immersed in pure water can be obtained.

Heretofore, the case of using the second layer as a layered product with a release film has been described, but a layered product of the second layer and the first layer, that is, a die-bonding film may be used. In this way, when the adhesive force of the die bonding film is measured, the strong adhesive tape is not attached to the exposed surface of the second layer, but is attached to the exposed surface of the first layer (the one on the opposite side of the second layer). noodle). In addition, when the test piece (the second layer) is cut into a strip shape, a notch can be formed in the entire region in the thickness direction of the die-bonding film (the entire region in the thickness direction of the first layer and the second layer), and the All the die-bonding films were cut into strips. In addition, as in the case of the second layer alone, the die-bonding film can be used as a laminate with the release film, and in this case, the release film can be removed at an appropriate timing.

The post-dipping adhesive force of the laminate for the test was measured as follows. That is, at normal temperature (eg, 23° C.), in this test laminate, the strong adhesive tape was stretched at a peeling (stretching) speed of 300 mm/min, and a peeling surface was produced in the test laminate. At this time, the strong adhesive tape is stretched at an angle of 180° between the newly generated peeling surfaces, that is, 180° peeling is performed. In other words, stretch one end of the strong adhesive tape toward the other. Then, the peeling force (load, N/25 mm) measured when the interface peeling between the cured object of the second layer and the mirror-surface silicon wafer occurred was used as the aforementioned post-immersion adhesive force (a test laminate immersed in pure water). Adhesion between the hardened material of the second layer with a width of 25mm in the body and the mirror-surface silicon wafer) is used. The strong adhesive tape can be stretched using, for example, a known tensile tester.

So far, the method for measuring the adhesive force (adhesion force after immersion) between the hardened object of the second layer of the test laminate immersed in pure water and the mirror-surface silicon wafer (post-immersion adhesive force) has been described. The same method can also be used to measure the adhesive force between the cured product of the second layer with a width of 25 mm and the mirror-surface silicon wafer (this specification is abbreviated as "laminated product for non-immersion test") in pure water. In the specification, it is referred to as "non-dipping adhesion") (N/25mm). The non-immersion adhesive force can be measured in the same manner as in the case of the above-mentioned post-immersion adhesive force, except that the test laminate which has not been immersed in pure water is used.

The laminate for non-immersion test, except that, for example, the mirror-surface silicon wafer with the cut test piece is left to stand for 30 minutes in a dark place in an air environment at a temperature of 23°C and a relative humidity of 50%. , except that the step of immersing in pure water at 23° C. for 2 hours was replaced by the same method as in the case of the aforementioned test layered body.

When measuring either the post-dipping adhesive force or the non-dipping adhesive force, in the peeling test described above, except for peeling at the interface between the cured object of the second layer and the mirror-surface silicon wafer (in this specification, referred to as "on the mirror surface" In addition to the peeling of the silicon wafer"), the interface peeling between the strong adhesive tape and its adjacent layers (for example, the cured product of the second layer, the first layer, etc.) Peeling"), cohesion failure of the cured product in the second layer, etc. may also occur. In the case where the adhesion between the hardened object of the second layer and the mirror-surface silicon wafer is very large, in the peel test, for example, except for the peel-off of the mirror-surface silicon wafer (the hardened object of the second layer and the mirror-surface silicon wafer) In addition to interfacial peeling between circles), peeling of the strong adhesive tape (interfacial peeling between the strong adhesive tape and its adjacent layer) easily occurs before the cohesion failure of the cured product of the second layer occurs. In this case, if the peeling force at the time of peeling of the strong adhesive tape is 6N/25mm or more, it can be judged that the adhesive force between the second layer cured product with a width of 25mm and the mirror-surface silicon wafer is 6N/25mm or more. On the other hand, when the adhesive force between the cured object of the second layer and the mirror-surface silicon wafer is small, peeling of the mirror-surface silicon wafer is likely to occur before the peeling of the strong adhesive tape occurs during the peeling test, for example. .

The adhesive force after dipping is above 6N/25mm, preferably above 7N/25mm, preferably above 8N/25mm, more preferably above 9N/25mm. When the adhesive force after immersion is greater than or equal to the aforementioned lower limit value, when a semiconductor wafer having a small size is picked up, the transferability of the cured product of the second layer to a semiconductor becomes high.

The upper limit of the adhesive force after the immersion is not particularly limited. For example, in the case of the cured product of the second layer whose adhesive force after immersion is 20 N/25 mm or less, it is easier to obtain the constituent raw materials.

The post-dipping adhesive force can be appropriately adjusted within the range set by any combination of the above-mentioned preferable lower limit value and upper limit value. For example, the adhesive force after dipping is preferably 6~20N/25mm, preferably 7~20N/25mm, more preferably 8~20N/25mm, and particularly preferably 9~20N/25mm. Moreover, on the other hand, 10-20N/25mm may be sufficient. However, these are only examples of the aforementioned post-dipping adhesion.

The non-dipping adhesive force is not particularly limited, but the post-dipping adhesive force is preferably equal to or greater than the same. For example, the non-dipping adhesive force is any one of 6N/25mm or more, 7N/25mm or more, 8N/25mm or more, and 9N/25mm or more, and the post-dipping adhesive force may be the same or more. Moreover, the said non-dipping adhesive force is 20 N/25mm or less, and the said post-dipping adhesive force may be equal to or more. Therefore, the non-dipping adhesive force may be any of 6-20N/25mm, 7-20N/25mm, 8-20N/25mm, and 9-20N/25mm, and the post-dipping adhesive force may be equal to or more than the same. Moreover, on the other hand, 10-20N/25mm may be sufficient.

On the other hand, in the die-bonding film according to one embodiment of the present invention, the second layer may have the characteristics of the post-dipping adhesion of 6 to 20 N/25 mm and the non-dipping adhesion of 6 to 20 N/25 mm.

The second layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of plural layers, these plural layers may be the same or different from each other. The combination of these plural layers is not particularly limited. limited.

The thickness of the second layer is not particularly limited, but is preferably 1 to 40 μm, preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. When the thickness of the second layer is greater than or equal to the aforementioned lower limit value, the adhesive force to the covering body (semiconductor wafer, semiconductor wafer) of the second layer becomes higher. As a result, when a small-sized semiconductor wafer is picked up, the second The transferability of the cured product of the layer to the semiconductor wafer becomes higher. When the thickness of the second layer is equal to or less than the above-mentioned upper limit value, the second layer (die bonding film) can be more easily cut in the semiconductor wafer manufacturing process described later, and the occurrence of cut pieces from the second layer can be reduced. quantity. Here, the "thickness of the second layer" refers to the thickness of the entire second layer, for example, the thickness of the second layer composed of a plurality of layers refers to the total thickness of all the layers constituting the second layer.

The second layer (second thin film) is formed of the second adhesive composition containing its constituent material. For example, the 2nd adhesive composition can be apply|coated to the formation object surface of a 2nd layer, and it can dry as needed, and a 2nd layer can be formed in a target site|part. The content ratio of the components that do not vaporize at room temperature in the second adhesive composition is usually the same as the content ratio of the components described above in the second layer.

The second adhesive composition may be applied by the same method as in the case of the first adhesive composition, and the drying conditions of the second adhesive composition may be the same as the drying conditions of the first adhesive composition. Next, the second adhesive composition will be described in detail.

>>Second Adhesive Composition>> The type of the second adhesive composition can be selected according to the properties of the second layer, such as the presence or absence of thermosetting properties of the second layer. The second adhesive composition has energy ray curability, and may have both energy ray curability and thermosetting properties. The components contained in the second adhesive composition and the second layer are the same as those contained in the above-described first adhesive composition and the first layer. Therefore, the effects achieved by the components contained therein are also the same as in the case of the first adhesive composition and the first layer. The second adhesive composition includes, for example, a polymer component (a), a filler (d), an energy ray thermosetting resin (g), and a photopolymerization initiator (h).

(polymer component (a)) The polymer component (a) in the second adhesive composition and the second layer is the same as the polymer component (a) in the first adhesive composition and the first layer.

The second adhesive composition and the polymer component (a) in the second layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

In the second adhesive composition, the content ratio of the polymer component (a) with respect to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (a) in the second layer) , regardless of the type of the polymer component (a), preferably 10 to 45 mass %, preferably 15 to 40 mass %, and particularly preferably 20 to 35 mass %.

In the second adhesive composition and the second layer, the ratio of the content of the acrylic resin to the total content (total mass) of the polymer component (a) is preferably 80 to 100 mass %, preferably 85 to 100 mass % Preferably, 90-100 mass % is more preferable, for example, 95-100 mass % may be sufficient.

(filler (d)) The filler (d) in the second adhesive composition and the second layer is the same as the filler (d) in the first adhesive composition and the first layer.

Only one type of filler (d) contained in the second adhesive composition and the second layer may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

In the second adhesive composition, the ratio of the content of the filler (d) with respect to the total content (total mass) of all components other than the solvent (that is, the content of the filler (d) in the second layer) is: 25-70 mass % is preferable, 35-67 mass % is preferable, and 45-64 mass % is especially preferable. When the content of the filler (d) is within such a range, it becomes easier to adjust the thermal expansion coefficient, moisture absorption rate, and heat release properties of the second layer.

When the filler (d) having an average particle size of 1 to 1000 nm is used, in the second adhesive composition and the second layer, the average particle size with respect to the total content (total mass) of the filler (d) is The content ratio of the filler (d) of 1 to 1000 nm is preferably 80 to 100 mass %, preferably 85 to 100 mass %, more preferably 90 to 100 mass %, and may be, for example, 95 to 100 mass %.

(Energy beam curable resin (g)) The energy ray curable resin (g) in the second adhesive composition and the second layer is the same as the energy ray curable resin (g) in the first adhesive composition and the first layer.

The energy ray-curable resin (g) contained in the second adhesive composition and the second layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected. In one aspect, the energy ray curable resin (g) contained in the second adhesive composition and the second layer is selected from the group consisting of tricyclodecane dimethylol diacrylate and ε-caprolactone modified gins-(2 At least one kind of acryloxyethyl) isocyanate is preferable.

In the second adhesive composition, the content of the energy ray-curable resin (g) is preferably 1 to 95 mass %, preferably 3 to 90 mass % with respect to the total mass of the second adhesive composition , 5~85% by mass is particularly preferred.

(Photopolymerization initiator (h)) The photopolymerization initiator (h) in the second adhesive composition and the second layer is the same as the photopolymerization initiator (h) in the first adhesive composition and the first layer.

The photopolymerization initiator (h) contained in the second adhesive composition and the second layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected. In one aspect, the photopolymerization initiator (h) in the second adhesive composition and the second layer is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) -Butanone-1 is preferred.

In the second adhesive composition and the second layer, the content of the photopolymerization initiator (h) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the energy ray-curable resin (g), 0.5-15 mass parts is preferable, and 1-10 mass parts is especially preferable.

In order to improve various physical properties, in addition to the polymer component (a), filler (d), energy ray thermosetting resin (g), and photopolymerization initiator (h), the second layer may further contain as needed Other ingredients that do not correspond to these. Other components contained in the second layer include, for example, a coupling agent (e), an epoxy-based thermosetting resin (b), a curing accelerator (c), a crosslinking agent (f), and a general-purpose additive (i) Wait. Among these, preferable other components mentioned above include, for example, a coupling agent (e) and a widely used additive (i).

(Couplant (e)) The second adhesive composition and the coupling agent (e) in the second layer are the same as the first adhesive composition and the coupling agent (e) in the first layer. In particular, the coupling agent (e) is preferably an oligomer type or polymer type organosiloxane.

Only one type of the coupling agent (e) contained in the second adhesive composition and the second layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and the ratio can be arbitrarily selected.

When the coupling agent (e) is used, in the second adhesive composition and the second layer, the content of the coupling agent (e) is 0.1 to 20 parts by mass relative to 100 parts by mass of the total content of the polymer component (a). Parts by mass are preferred, those of 0.5 to 15 parts by mass are preferred, and those of 1 to 10 parts by mass are particularly preferred. When the above-mentioned content of the coupling agent (e) is more than the above-mentioned lower limit value, the dispersibility to the resin of the filler (d) is improved, the adhesion of the covering body of the second layer is improved, etc., and the use of the coupling agent (e) can be obtained. more pronounced effect. When the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of outgas is suppressed more.

In the case where the coupling agent (e) is the aforementioned oligomer type or polymer type organosiloxane, in the second adhesive composition and the second layer, relative to the total content (total mass) of the coupling agent (e) ), the content ratio of the aforementioned oligomer type or polymer type organosiloxane may be any of 25-100 mass % and 40-100 mass %.

(Epoxy-based thermosetting resin (b) (epoxy resin (b1) and thermosetting agent (b2)) The epoxy-based thermosetting resin (b) consists of an epoxy resin (b1) and a thermosetting agent (b2). The second adhesive composition and the epoxy-based thermosetting resin (b) in the second layer (epoxy resin (b1), thermosetting agent (b2)), and the first adhesive composition and the first layer The epoxy-based thermosetting resin (b) (epoxy resin (b1), thermosetting agent (b2)) is the same.

Each of the epoxy resin (b1) and the thermosetting agent (b2) contained in the second adhesive composition and the second layer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio may be different. Arbitrary choice.

When an epoxy resin (b1) and a thermosetting agent (b2) are used, the content of the thermosetting agent (b2) in the second adhesive composition and the second layer is relative to the content of the epoxy resin (b1) 100 parts by mass, preferably 10 to 200 parts by mass. When the said content of a thermosetting agent (b2) is more than the said lower limit, hardening of a 2nd layer becomes easier. When the said content of a thermosetting agent (b2) is below the said upper limit, the moisture absorption rate of a 2nd layer falls, and the reliability of the package which uses a 2nd layer is improved more.

In the case of using an epoxy resin (b1) and a thermosetting agent (b2), the content of the epoxy-based thermosetting agent (b) in the second adhesive composition and the second layer (epoxy resin (b1) and The total content of the thermosetting agent (b2) is preferably 400 to 1200 parts by mass relative to 100 parts by mass of the content of the polymer component (a). When the said content of an epoxy-type thermosetting agent (b) is such a range, it becomes easier to adjust the adhesive force of a 2nd layer.

(hardening accelerator (c)) When the second adhesive composition and the second layer contain the epoxy-based thermosetting resin (b), it is preferable to contain the curing accelerator (c). The curing accelerator (c) in the second adhesive composition and the second layer is the same as the curing accelerator (c) in the first adhesive composition and the first layer.

Only one type of curing accelerator (c) contained in the second adhesive composition and the second layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and ratio can be arbitrarily selected.

In the case of using a curing accelerator (c), the content of the curing accelerator (c) in the second adhesive composition and the second layer is 100 parts by mass relative to the content of the epoxy-based thermosetting agent (b) in 100 parts by mass, The content of 0.01 to 5 parts by mass is preferred, and the content of 0.1 to 2 parts by mass is preferred. When the said content of a hardening accelerator (c) is more than the said lower limit, the effect more remarkable by using a hardening accelerator (c) can be acquired. If the content of the curing accelerator (c) is below the upper limit value, for example, a highly polar curing accelerator (c) is suppressed from moving to the interface side with the coating in the second layer under high temperature and high humidity conditions The effect of segregation is increased, and the reliability of the package obtained by using the second layer is further improved.

(Crosslinker (f)) The crosslinking agent (f) in the second adhesive composition and the second layer is the same as the crosslinking agent (f) in the first adhesive composition and the first layer.

Only one type of the crosslinking agent (f) contained in the second adhesive composition and the second layer may be used, or two or more types may be sufficient, and in the case of two or more types, the combination and the ratio thereof can be arbitrarily selected.

In the second adhesive composition and the second layer, the content of the crosslinking agent (f) is preferably 0 to 5 parts by mass relative to 100 parts by mass of the content of the polymer component (a).

(General Additive (i)) The general additive (i) in the second adhesive composition and the second layer is the same as the general additive (i) in the first adhesive composition and the first layer.

The general additive (i) contained in the second adhesive composition and the second layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected. The content of the second adhesive composition and the widely used additive (i) of the second layer is not particularly limited, and may be appropriately selected depending on the purpose.

(solvent) It is preferable that the second adhesive composition further contains a solvent. The second adhesive composition containing the solvent has good handleability. The solvent in the second adhesive composition is the same as the solvent in the first adhesive composition.

The solvent contained in the second adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the second adhesive composition can be mixed more uniformly.

One of preferable second adhesive compositions includes, for example, a polymer component (a), a filler (d), an energy ray thermosetting resin (g), a photopolymerization initiator (h), and As for the coupling agent (e), in addition to these, those further containing the widely-used additive (i) can be mentioned.

>>Manufacturing method of 2nd adhesive composition>> The second adhesive composition can be produced by the same method as in the case of the above-mentioned first adhesive composition.

The thickness of the die-bonding film (the total thickness of the first layer and the second layer) is preferably 2 to 80 μm, more preferably 6 to 60 μm, and particularly preferably 10 to 40 μm.

FIG. 1 is a cross-sectional view schematically showing a die-bonding thin film according to an embodiment of the present invention. In addition, in order to facilitate understanding of the characteristics of the present invention, the drawings used in the following description may have main parts enlarged for convenience of display, and the dimensional ratios and the like of each component are not necessarily the same as the actual ones.

The die-bonding thin film 13 shown here has a first layer 131 and a second layer 132 on the first layer 131 . The die-bonding film 13 has a first release film 151 on one side (referred to as a "first side" in this specification) 13a, and has a second side (referred to as a "second side" in this specification) on the opposite side of the first side 13a. ) 13b has a second release film 152. Such a die-bonding film 13 is preferably stored as a roll, for example.

In the die-bonding film 13 , a first release film 151 is laminated on a surface 132 a (referred to as a “first surface” in this specification) on the opposite side of the second layer 132 and the first layer 131 , and a first release film 151 is laminated on the first layer 131 The second release film 152 is laminated on the surface 131b opposite to the second layer 132 side (referred to as a "second surface" in this specification). The second surface 131 b of the first layer 131 is the same as the second surface 13 b of the die-bonding film 13 , and the first surface 132 a of the second layer 132 is the same as the first surface 13 a of the die-bonding film 13 .

In the die-bonding film 13, the initial detection temperature (T ₀ ) of the first layer is 75° C. or lower. In the die-bonding film 13, the second layer has adhesiveness and energy ray curability, and the post-dipping adhesive force of the laminated body for testing produced using the test piece of the second layer is 6 N/25 mm or more.

Both the first release film 151 and the second release film 152 may be known ones. The first peeling film 151 and the second peeling film 152 may be the same or different from each other, for example, the peeling force required for peeling from the die-bonding film 13 may be different from each other.

The die-bonding film 13 shown in FIG. 1 is attached to the back surface of a semiconductor wafer (not shown) on the exposed surface by removing the first release film 151 , in other words, the first surface 132 a of the second layer 132 . . Then, the surface exposed by the removal of the second release film 152, in other words, the second surface 131b of the first layer 131, becomes the surface to which the support sheet described later is attached.

◇Manufacturing method of die bonding film For example, the die-bonding film can be produced by forming the first layer (first film) and the second layer (second film) separately, and then laminating the two layers. The method for forming the first layer and the second layer is as follows: previously explained.

For example, on the release film, the first layer is formed in advance using the first adhesive composition, and similarly, the second layer is formed in advance using the second adhesive composition on the release film. In this case, it is preferable that these compositions are applied to the release-treated surface of the release film. Then, the exposed surface on the opposite side of the contact side of the release film of the first layer already formed is bonded to the exposed surface of the second layer already formed on the opposite side of the contact side of the release film to obtain a laminated first layer and the second-layer die-bonding film. The release film in contact with the first layer and the release film in contact with the second layer can be removed at an appropriate timing when the die bonding film is used.

◇Cutting die bonding pads A dicing die-bonding sheet according to an embodiment of the present invention includes a support sheet, the die-bonding film is provided on the support sheet, and the first layer in the die-bonding film is disposed on the support sheet side. The aforementioned dicing die-bonding sheet can be used in dicing of semiconductor wafers. Hereinafter, each layer constituting the dicing die-bonding sheet will be described in detail.

◎Support film The aforementioned support sheet may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the support sheet is composed of plural layers, the constituent materials and thicknesses of these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited as long as the effect of the present invention is not impaired.

As a preferable support sheet, for example, the thing which consists only of a board|substrate, the thing which has a base material, and the thing which has an intermediate layer on the said base material, etc. can be mentioned.

The aforementioned support sheet consisting only of the base material is suitable as a carrier sheet or a dicing sheet. A dicing die-bonding sheet having a support sheet composed of only such a base material is attached to the semiconductor wafer on the opposite side (ie, the first face) of the support sheet (ie, base material) side having the die-bonding film. Use for the back of the circle.

On the other hand, the said support sheet which has a base material and has an intermediate layer on the said base material is suitable as a dicing sheet. The dicing die-bonding sheet having such a support sheet is also used by being attached to the back surface of the semiconductor wafer on the opposite side (ie, the first face) of the support sheet side having the die-bonding film.

The method of using the dicing die-bonding sheet will be described in detail later. The layers constituting the support sheet will be described below.

○Substrate The said base material is a sheet form or a film form, and its constituent material, for example, various resins are mentioned. For example, the aforementioned resins include polyethylenes such as low-density polyethylene (abbreviated as LDPE), linear low-density polyethylene (abbreviated as LLDPE), high-density polyethylene (abbreviated as HDPE), etc.; polypropylene, polybutene, Polyolefins other than polyethylene such as polybutadiene, polymethylpentene, and norbornene resins; ethylene-vinyl acetate copolymer, ethylene-(methane)acrylic acid copolymer, ethylene-(methyl) Vinyl-based copolymers such as acrylate copolymers and ethylene-norbornene copolymers (copolymers using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using vinyl chloride as a monomer) polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, poly Polyesters such as wholly aromatic polyesters in which all constituent units of ethylene 2,6-naphthalenedicarboxylate have aromatic ring groups; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates ; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Moreover, the said resin, for example, the polymer mixture of the mixture of the said polyester and resin other than it, etc. can also be mentioned. It is preferable that the polymerized mixture of the above-mentioned polyester and resins other than polyesters has a relatively small amount of resins other than polyesters. In addition, the aforementioned resins include, for example, cross-linked resins crosslinked using one or more of the aforementioned resins exemplified so far; ionic polymers of one or more of the aforementioned resins exemplified so far, etc. of modified resins.

There may be only one type of resin constituting the base material, or two or more types may be sufficient, and in the case of two or more types, the combination and the ratio thereof can be arbitrarily selected.

The base material may be composed of one layer (single layer), or may be composed of two or more plural layers. When composed of plural layers, these plural layers may be the same or different from each other. The combination of these plural layers does not Specially limited.

The thickness of the substrate is preferably 50-300 μm, and preferably 60-150 μm. When the thickness of the base material is in such a range, the flexibility of the dicing die-bonding sheet, the adhesion of the dicing die-bonding sheet to a semiconductor wafer or a semiconductor wafer, and the semiconductor with a cured die-bonding film described later The pick-up performance of the chip is even more improved. Here, the "thickness of the base material" means the thickness of the entire base material, for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

The base material is preferably one that has high accuracy in thickness, that is, one that suppresses variation in thickness regardless of the location. Among the above-mentioned constituent materials, as the materials that can be used to form the base material having such a high thickness and accuracy, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, polyethylene terephthalate can be mentioned. Butylene formate, urethane acrylate, ethylene-vinyl acetate copolymer, etc.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like, in addition to the main constituent materials of the aforementioned resins.

The substrate can be transparent or opaque, and can be visually colored, and other layers can also be vapor deposited. However, the substrate is preferably one that transmits energy rays, and is preferably one that has high energy ray permeability.

In order to improve the adhesion with other layers such as the intermediate layer provided thereon, the surface of the substrate may be subjected to roughening treatment by sandblasting, solvent treatment, etc., corona discharge treatment (corona discharge treatment), electron beam Irradiation treatment, plasma treatment, ozone ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, etc. In addition, a primer treatment may be performed on the surface of the substrate. Also, the base material may have an antistatic coating; a layer that prevents the base material from adhering to other sheets, the base material and an adsorption table (adsorption table) adhering layer, and the like, when the dicing die-bonding sheet is stored for stacking.

The base material can be produced by a known method. For example, the resin-containing base material can be produced by molding the resin composition containing the aforementioned resin.

○Intermediate layer The said intermediate layer is arrange|positioned between a base material and a die-bonding thin film, and will not be specifically limited if it can exhibit its function. More specific examples of the intermediate layer include a peelability-improving layer, an adhesive layer, etc. whose at least one side has been subjected to a peeling treatment.

The said peelability improvement layer makes it easy to peel the hardened die-bonding film from the support sheet when the semiconductor wafer with the hardened die-bonding film mentioned later is picked up. The aforementioned adhesive layer stabilizes the fixation of the semiconductor wafer on the support sheet during dicing, or allows the cured die-bonding film to be easily removed from the support sheet when the semiconductor wafer with the cured die-bonding film is picked up. stripped.

‧Peelability improvement layer The said peelability improvement layer is a sheet form or a film form. The peelability improvement layer is formed of, for example, a plurality of layers having a resin layer and a peeling treatment layer formed on the resin layer, a single layer including a peeling layer, and the like. In the dicing die-bonding sheet, the peelability-improving layer is disposed on the side of the peeling-treated die-bonding film.

Among the peelability-improving layers composed of a plurality of layers, the resin layer can be produced by molding or coating a resin composition containing a resin, and drying it as necessary. Then, the peelability improvement layer which consists of a plurality of layers can be manufactured by subjecting one surface of the resin layer to a peeling treatment.

The peeling process of the said resin layer can be performed with various well-known release agents, such as an alkyd type, a silicone type, a fluorine type, an unsaturated polyester type, a polyolefin type, or a wax type, for example. The aforementioned release agent is preferably an alkyd-based, silicone-based or fluorine-based release agent from the viewpoint of having heat resistance.

The resin used as the constituent material of the resin layer can be appropriately selected depending on the purpose, and is not particularly limited. The aforementioned resins are preferably, for example, polyethylene terephthalate (abbreviated as PET), polyethylene naphthalate (abbreviated as PEN), polybutylene terephthalate (abbreviated as PBT), poly(ethylene terephthalate) Ethylene (referred to as PE), polypropylene (referred to as PP), etc.

The above-mentioned resin layer may be composed of one layer (single layer), or may be composed of two or more plural layers. When composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited. .

The releasability-improving layer composed of a single layer can be produced by molding or applying a release agent composition containing a release agent, and drying it as necessary. As a release agent contained in the said peelable composition, the thing similar to the said various release agent used at the time of the peeling process of the said resin layer is mentioned. The said peelable composition may contain the same resin as the resin which is a constituent material of the said resin layer. That is, the releasability-improving layer consisting of a single layer may contain resin in addition to the release agent.

The thickness of the peelability improving layer is preferably 10 to 200 μm, more preferably 15 to 150 μm, and particularly preferably 25 to 120 μm. When the thickness of the releasability-improving layer is greater than or equal to the aforementioned lower limit value, the effect of the releasability-improving layer becomes more prominent, and the effect of suppressing breakage such as cutting of the releasability-improving layer becomes higher. When the thickness of the peelability improving layer is below the aforementioned upper limit value, when the semiconductor wafer with the hardened die-bonding film is picked up, the upward force is easily transmitted to the semiconductor wafer with the hardened die-bonding film. Easy to pick up. Here, the "thickness of the releasable improvement layer" means the total thickness of the resin layer and the release-treated layer when the releasable-improved layer is composed of a plurality of layers including the resin layer and the release-treated layer. In addition, when the peelability improvement layer consists of a single layer containing a release agent, the thickness of this single layer is shown.

‧Adhesive layer The aforementioned adhesive layer is in the form of a sheet or a film, and contains an adhesive. The aforementioned adhesives include, for example, adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins. Acrylic resins are preferred.

In addition, in this specification, "adhesive resin" refers to a concept that includes both a resin having adhesiveness and a resin having adhesiveness. For example, resin itself not only has adhesiveness, but also includes other components such as additives that are used in combination. Adhesive resins, resins exhibiting adhesiveness due to the presence of triggers such as heat or water, and the like.

The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of plural layers, these plural layers may be the same or different from each other. The combination of these plural layers There is no particular limitation.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

The adhesive layer may be transparent or opaque, and may be colored according to the purpose. However, the adhesive layer is preferably one that transmits energy rays, and is preferably one that has high energy ray permeability.

The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. The adhesive layer formed using the energy ray-curable adhesive can easily adjust the physical properties before and after curing.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed on a target site by applying an adhesive composition on the surface to be formed of the adhesive layer, and drying it if necessary.

Heretofore, the method for forming the releasability-improving layer and the adhesive layer has been described, but the present invention is not limited to this, and the intermediate layer can be formed using the composition for intermediate layers containing the constituent materials thereof. For example, the composition for an intermediate layer is applied to the surface to be formed of the intermediate layer, and if necessary, it is dried to form the intermediate layer at the target site. In addition, depending on the type of the composition for an intermediate layer, even if it is molded, an intermediate layer can be formed.

Next, an example of the dicing die-bonding sheet of the present invention will be described below with reference to the drawings for each type of support sheet.

FIG. 2 is a cross-sectional view schematically showing an embodiment of the dicing die-bonding sheet of the present invention. In addition, in the figures after FIG. 2, the same components as those shown in the figures already described are denoted by the same reference numerals as those in the figures already described, and the detailed description thereof will be omitted.

The dicing die-bonding sheet 1A shown here has a support sheet 10 and a die-bonding film 13 on the support sheet 10 . The support sheet 10 is formed only from the base material 11 , in other words, the dicing die-bonding sheet 1A has a structure in which the die-bonding film 13 is laminated on one side (referred to as “first side” in this specification) 11 a of the base material 11 . Moreover, the dicing die-bonding sheet 1A further has the release film 15 on the die-bonding film 13 .

In the dicing die-bonding sheet 1A, the first layer 131 is laminated on the first surface 11 a of the base material 11 . In addition, the second layer 132 is laminated on a surface (referred to as a "first surface" in this specification) 131a on the opposite side to the base material 11 side of the first layer 131 . In addition, on a part of the first surface 132a of the second layer 132 (in other words, the first surface 13a of the die-bonding film 13 ), that is, in the region near the edge, the mold adhesive layer 16 is laminated. Further, among the first surfaces 132 a of the second layer 132 , the surfaces on which the mold adhesive layer 16 is not laminated, and the surfaces 16 a (top and side surfaces) that are not in contact with the die-bonding film 13 among the mold adhesive layers 16 . , and the release film 15 is laminated. Here, the first surface 11 a of the base material 11 is also referred to as the first surface 10 a of the support sheet 10 .

The release film 15 is the same as the first release film 151 or the second release film 152 shown in FIG. 1 .

The adhesive layer 16 for a mold may be, for example, a single-layer structure containing an adhesive component, or a plural-layer structure in which layers containing the adhesive component are layered on both surfaces of the sheet forming the core material.

The dicing die-bonding sheet 1A is in a state in which the release film 15 is removed, and in the first surface 132a of the second layer 132 (the first surface 13a of the die-bonding film 13 ), the region where the mold adhesive layer 16 is not laminated A mold such as a ring frame is attached to the upper surface of the surface 16a of the adhesive layer 16 for molds by adhering to the back surface of the semiconductor wafer (not shown in the drawings).

FIG. 3 is a cross-sectional view schematically showing another embodiment of the dicing die-bonding sheet of the present invention. The dicing die-bonding sheet 1B shown here is the same as the dicing die-bonding sheet 1A shown in FIG. 2 except that it does not have the adhesive layer 16 for a mold. That is, in the dicing die-bonding sheet 1B, the first layer 131 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10 ), and the second layer 131 is laminated on the first surface 131a of the first layer 131 In the layer 132, the release film 15 is laminated on the entire surface of the first surface 132a of the second layer 132. In other words, the dicing die-bonding sheet 1B is constituted by laminating the base material 11 , the first layer 131 , the second layer 132 , and the release film 15 in this order in the thickness direction.

The dicing die-bonding sheet 1B shown in FIG. 3 is the same as the case of the dicing die-bonding sheet 1A shown in FIG. 2, in the state where the release film 15 is removed, the first surface 13a of the die-bonding film 13 is Parts of the middle and central regions are attached to the backside of the semiconductor wafer (not shown in the figure), and the region near the edge of the die-bonding film 13 is attached to a mold such as a ring frame and used.

FIG. 4 is a cross-sectional view schematically showing another embodiment of the dicing die-bonding sheet of the present invention. The dicing die-bonding sheet 1C shown here has the intermediate layer 12 between the base material 11 and the die-bonding film 13 (the first layer 131 ), and the dicing die-bonding sheet 1A shown in FIG. 2 same. The support sheet 10 is a laminate of the base material 11 and the intermediate layer 12 , and the dicing die-bonding sheet 1C also has a structure in which the die-bonding film 13 is laminated on the first surface 10 a of the support sheet 10 .

In the dicing die-bonding sheet 1C, the intermediate layer 12 is laminated on the first surface 11 a of the base material 11 . In addition, the first layer 131 is laminated on the surface (referred to as "first surface" in this specification) 12a of the intermediate layer 12 on the opposite side of the base material 11 side. Moreover, the 2nd layer 132 is laminated|stacked on the 1st surface 131a of the 1st layer 131. In addition, a part of the first surface 132a of the second layer 132 (in other words, the first surface 13a of the die-bonding film 13 ), that is, a region near the edge, is the adhesive layer 16 for a build-up mold. Further, among the first surfaces 132 a of the second layer 132 , the surfaces on which the mold adhesive layer 16 is not laminated, and among the mold adhesive layers 16 , the surfaces 16 a (top and side surfaces) that are not in contact with the die-bonding film 13 , and the release film 15 is laminated.

In the dicing die-bonding sheet 1C, when the intermediate layer 12 is the aforementioned releasability-improving layer composed of a plurality of layers, for example, the layer on the base material 11 side of the intermediate layer 12 is the aforementioned resin layer (not shown in the drawings) , the layer on the die-bonding film 13 (first layer 131 ) side of the intermediate layer 12 is the aforementioned peeling treatment layer (not shown in the drawings). Therefore, in this case, the 1st surface 12a of the intermediate layer 12 becomes a peeling process surface. On the other hand, when the intermediate layer 12a is a single layer constituting the aforementioned vitrity-improving layer, the first surface 12a of the intermediate layer 12 becomes the peeling-treated surface, which is the same as the above, except that the intermediate layer 12 all contains a release agent. When the intermediate layer 12 is the releasability-improving layer, the hardened die-bonding film can be easily peeled off when a semiconductor wafer with the hardened die-bonding film is picked up (the die-bonding film in FIG. 4 ). 13 is cut, and the second layer 132 in the die-bonding film 13 is further cured by energy rays).

In the dicing die-bonding sheet 1C shown in FIG. 4, in the state where the release film 15 is removed, the mold is not laminated on the first surface 132a of the second layer 132 (the first surface 13a of the die-bonding film 13). The area with the adhesive layer 16 is used by attaching the back surface of the semiconductor wafer (not shown in the figure), and by attaching a mold such as a ring frame to the upper surface of the surface 16a of the adhesive layer 16 for molds.

FIG. 5 is a cross-sectional view schematically showing another embodiment of the dicing die-bonding sheet of the present invention. The dicing die-bonding sheet 1D shown here is the same as the dicing die-bonding sheet 1C shown in FIG. 4 except that it does not have the mold adhesive layer 16 and that the shape of the die-bonding film is different. That is, the dicing die-bonding sheet 1D has the base material 11 , has the intermediate layer 12 on the base material 11 , and has the die-bonding thin film 23 on the intermediate layer 12 . The support sheet 10 is a laminate of the base material 11 and the intermediate layer 12 . The die-bonding film 23 is a laminate of the first layer 231 and the second layer 232 . The dicing die-bonding sheet 1D also has a structure in which the die-bonding thin film 23 is laminated on the first surface 10 a of the support sheet 10 .

In the dicing die-bonding sheet 1D, the intermediate layer 12 is laminated on the first surface 11 a of the base material 11 . Moreover, the 1st layer 231 is laminated|stacked in a part of the 1st surface 12a of the intermediate|middle layer 12, ie, the area|region on the center side. Moreover, the 2nd layer 231 is laminated|stacked on the 1st surface 231a of the 1st layer 231. Then, in the first surface 12a of the intermediate layer 12, the region where the die-bonding film 23 is not laminated, and on the surface of the die-bonding film 23 that is not in contact with the intermediate layer 12 (the first surface 23a and the side surface), The release film 15 is laminated.

When the die-bonding sheet 1D is diced from the top-down plane, the surface area of the die-bonding film 23 is smaller than that of the intermediate layer 12, and, for example, has a circular shape or the like.

In the dicing die-bonding sheet 1D shown in FIG. 5 , a semiconductor die is attached to the first surface 232 a of the second layer 232 (the first surface 23 a of the die-bonding film 23 ) in a state in which the release film 15 is removed. The back surface of the circle (not shown in the figure) is used by attaching a mold such as a ring frame to the first surface 12a of the intermediate layer 12 in the region where the die bonding film 23 is not laminated.

In addition, in the dicing die-bonding sheet 1D shown in FIG. 5 , in the first surface 12 a of the intermediate layer 12 , the region where the die-bonding film 23 is not laminated may be as shown in FIGS. 2 and 4 . In the same way, the adhesive layer for the mold is laminated (omitted in the drawing). The dicing die-bonding sheet 1D having such a mold-adhesive layer is attached to the upper surface among the surfaces of the mold-adhesive layer, as in the case of the dicing die-bonding sheet shown in FIGS. 2 and 4. It is used as a mold for ring frames and the like.

In this way, when the die-bonding sheet is diced, it is preferable that the support sheet and the die-bonding film have an adhesive layer for a mold regardless of the form of the support sheet and the die-bonding film. However, as shown in FIGS. 2 and 4 , in general, a dicing die-bonding sheet having a die-bonding adhesive layer is preferable to have a die-bonding film on the die-bonding film.

The dicing die-bonding sheet of the present invention is not limited to those shown in FIGS. 2 to 5, and a part of the configuration shown in FIGS. Other components may be added to those described so far.

For example, in the dicing die-bonding sheet shown in FIGS. 2 to 5 , layers other than the base material, the intermediate layer, the die-bonding film, and the release film may be provided at arbitrary positions. In addition, in the dicing die-bonding sheet, a partial gap may be generated between the release film and the layer in direct contact with the release film. In addition, in the dicing die-bonding sheet, the size, shape, and the like of each layer can be arbitrarily adjusted depending on the purpose.

◇Manufacturing method of dicing die bonding sheet The dicing die-bonding sheet can be produced, for example, by bonding the aforementioned die-bonding film and the support sheet.

The support sheet which has a base material and an intermediate layer can be manufactured by apply|coating the said composition for intermediate layers on a base material, and drying as needed. For example, when the intermediate layer is a peelability-improving layer, the composition for an intermediate layer for forming the resin layer may be applied to the substrate, and the exposed surface may be peeled after the resin layer is formed.

The support sheet which has a base material and an intermediate layer can also be manufactured by the following method. That is, except that the base material is replaced with a release film, the intermediate layer is first formed on the release film in the same method as in the case of the above-described method of forming the intermediate layer. In this case, the composition for an intermediate layer is preferably applied to the release-treated surface of the release film. After that, the exposed surface of the intermediate layer (surface on the opposite side to the release film side) and one surface (first surface) of the base material are bonded together to manufacture the above-mentioned support sheet.

In addition, the dicing die-bonding sheet can be produced, for example, without forming the above-mentioned die-bonding film and support sheet in advance. For example, in the above-described method, an intermediate layer is formed on the release film in advance. Furthermore, using the first layer (first thin film) already formed on the release film, the second layer (second thin film) already formed on the release film, and the base material, the base material, the formed intermediate layer, the already formed The formed first layer and the already formed second layer are laminated in this order in the thickness direction. At this time, the said release film provided in each layer is removed at an appropriate timing as needed. According to the above, a dicing die-bonding sheet having an intermediate layer can be obtained.

◇Manufacturing method of semiconductor wafer The die-bonding film and the dicing die-bonding sheet of the present invention can be used for the manufacture of semiconductor wafers, more specifically, for the manufacture of semiconductor wafers with hardened die-bonding films.

A method of manufacturing a semiconductor wafer according to an embodiment of the present invention includes: forming a laminated body (1-1) in which the semiconductor wafer is attached to the second layer and the dicing sheet is attached to the first layer in the die-bonding film, or In the aforementioned dicing die-bonding sheet, the step of attaching the second layer of the semiconductor wafer laminate (1-2) in the die-bonding film (in this specification, referred to as "the laminate (1) fabrication step") ); with a dicing knife, by cutting the semiconductor wafer and the die-bonding film in the laminate (1-1) or the laminate (1-2) together, the first layer having the first layer after cutting, The step of forming the layered body (2) of the second layer after cutting and the semiconductor wafer (semiconductor wafer after cutting) (in this specification, referred to as "the layered body (2) production step"); Steps of producing a layered body (3) having the cut first layer, the cured product, and the semiconductor wafer by energy ray curing of the cut second layer in the body (2) to form a cured product (this specification , referred to as the "layered body (3) production step"); and the semiconductor wafer having the cut first layer and the cured product in the layered body (3) is separated from the dicing sheet or the support sheet, The step of picking up (referred to as "picking step" in this specification). In addition, in this specification, the laminated body (1-1) and the laminated body (1-2) are included, and are called "laminated body (1)".

In the above-mentioned manufacturing method, since the above-mentioned die-bonding film or dicing die-bonding sheet is used, even if the size of the semiconductor wafer is small, in the above-mentioned pick-up step, the cured product of the second layer after cutting (the cut and cured second layer) Part or all of the two layers), peeling from the semiconductor wafer is suppressed, and the transferability of the cured product of the second layer to the semiconductor wafer is high.

Hereinafter, the aforementioned manufacturing method will be described in detail with reference to the drawings. FIG. 6 is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. Here, the manufacturing method of the semiconductor wafer in the case of using the dicing die-bonding sheet 1A shown in FIG. 2 is demonstrated.

>>Laminated body (1) production steps>> In the above-mentioned production step of the laminated body (1), as shown in FIG. 6, the second layer 132 of the die-bonding sheet 1A and the die-bonding film 13 are diced, and the semiconductor wafer 9 is attached to form a laminated body ( 1-2) 101. The laminate (1-2) 101 is composed of the base material 11, the first layer 131, the second layer 132, and the semiconductor wafer 9 (in other words, the base material 11, the die-bonding film 13, and the semiconductor wafer 9). It is constituted by stacking layers sequentially in the thickness direction.

In the laminated body (1-2) 101, the back surface 9b of the semiconductor wafer 9 is attached to the first surface 132a of the second layer 132. The dicing die-bonding sheet 1A is used by removing the release film 15 .

Here, the case where the dicing die-bonding sheet 1A is used will be described, but in this step, the die-bonding film 13 may be used without the dicing die-bonding sheet 1A, and the second layer 132 may be attached to the die-bonding film 13. The semiconductor wafer 9 is a laminate (1-1) in which the base material 11 (support sheet 10) is attached to the first layer 131 as a dicing sheet. The laminate (1-1) is composed of the base material 11, the first layer 131, the second layer 132, and the semiconductor wafer 9 (in other words, the base material 11, the die-bonding film 13, and the semiconductor wafer 9) in accordance with the It consists of layers stacked in order in its thickness direction. In this way, the obtained layered body (1-2) and the layered body (1-1) are identical in appearance, and both can be described as layered body (1) 101.

The attachment of the semiconductor wafer 9 to the second layer 132 may be performed by heating and softening the second layer 132 . In this case, the heating temperature of the second layer 132 is preferably 35 to 45°C. In addition, when attaching the semiconductor wafer 9 to the second layer 132, the attaching speed and the attaching pressure are not particularly limited. For example, the sticking speed is preferably 5~20mm/s, and the sticking pressure is preferably 0.1~1.0MPa.

When the die-bonding film 13 is used without the dicing die-bonding sheet 1A, after the dicing sheet (the base material 11 and the support sheet 10 ) is attached to the first layer 131 , the semiconductor wafer is attached to the second layer 132 . 9 is better. The attaching of the dicing sheet to the first layer 131 can be performed by a known method, and for example, the same conditions as when attaching the semiconductor wafer 9 can be used.

>>Laminated body (2) production steps>> In the above-mentioned production step of the layered body (2), the semiconductor wafer 9 in the layered body (1) 101 and the die-bonding film 13 (ie, the first layer 131 and the second layer 132 ) in the layered body (1) 101 are joined together using a dicing blade. As shown in FIG. 6 , the layered body ( 2 ) 102 having the first layer 131 ′ after cutting, the second layer 132 ′ after cutting, and the semiconductor wafer 9 ′ is produced by cutting. In the laminated body (2) 102, the first layer 131' after cutting, the second layer 132' after cutting, and the semiconductor wafer 9' (in other words, the die-bonding film 13' and the semiconductor wafer 9' after cutting) depend on each other. The plurality of laminates stacked in order in the thickness direction are fixed in an aligned state on the base material 11 via the first layer 131 ′. In Fig. 6(b), the die-bonding film 13 and the dicing die-bonding sheet 1A after cutting are denoted by a new symbol 1A'.

In this step, generally, dicing is performed while running water (dicing water) at the contact position between the dicing blade and the semiconductor wafer 9 . At this time, the adhesion and adhesion between the first surface 132a of the second layer 132 and the back surface 9b of the semiconductor wafer 9 are high, because the first surface 132a' of the second layer 132' and the semiconductor wafer 9' after cutting Since the adhesive force and adhesiveness of the back surface 9b' are high, the intrusion of water into these contact surfaces is suppressed.

The size of the semiconductor wafer 9' produced in this step is not particularly limited, but the length of one side of the semiconductor wafer 9' is preferably 0.1 to 2.5 mm. When the semiconductor wafer 9' of such a small size is produced, the effect of the present invention can be obtained more remarkably.

The cutting conditions can be appropriately adjusted depending on the purpose and are not particularly limited. Usually, the rotation speed of the cutting blade is preferably 15000~50000rpm, and the moving speed of the cutting blade is preferably 5~75mm/sec.

At the time of dicing, the base material 11 may be cut to a depth of, for example, about 30 μm or less from the first surface 11 a of the base material 11 with a dicing blade.

>>Laminated body (3) production steps>> In the above-mentioned production step of the layered body (3), a cured product 1320' is formed by energy ray curing of the second layer 132' after cutting in the layered body (2) 102, as shown in Fig. 6(c). , which has the layered body (3) 103 of the cut first layer 131', the cured product 1320', and the semiconductor wafer 9'. In the laminated body (3) 103, the first layer 131' after cutting, the second layer 1320' after cutting and hardening, and the semiconductor wafer 9' are laminated in this order in the thickness direction. The first layer 131 ′ is fixed on the base material 11 in an aligned state. The layered body (3) 103 is the same as the layered body (2) 102 except that the second layer 132' after cutting is cured.

Here, a laminate of the first layer 131' after cutting and the second layer 1320' after cutting and hardening is represented by reference numeral 130'. In this specification, the laminate from such a die-bonding film 13 is referred to as a "hardened die-bonding film".

As described above, the adhesive force and adhesion between the second layer 132' after cutting and the semiconductor wafer 9' are high, but since the second layer 132' after cutting becomes the cured product 1320', the cured product 1320' and the semiconductor wafer 9' Adhesion and adhesion of 9' became higher.

When irradiating the cut second layer 132' with energy rays to harden the second layer 132' with energy rays, the irradiation conditions of the energy rays are not particularly limited as long as the energy rays are sufficient to harden the second layer 132'. For example, when the energy ray is hardened, the illuminance of the energy ray is preferably 4~280mW/cm ² . When the energy ray is hardened, the light quantity of the energy ray is preferably 3 to 1000 mJ/cm ² . The energy ray is preferably irradiated from the substrate 11 side, through the substrate 11 and the first layer 131' after cutting, and irradiating the second layer 132' after cutting.

>>Pick up steps>> In the aforementioned pickup step, as shown in FIG. 6(d), in the laminated body (3) 103, the semiconductor wafer 9' having the cut first layer 131' and the aforementioned cured product 1320' is removed from the support sheet 10. (Substrate 11) Separation and pickup. In this specification, such a semiconductor wafer is called "semiconductor wafer with a hardened die-bonding film".

As described above, even if the size of the semiconductor wafer 9' is small, since the second layer 132' and the semiconductor wafer 9' after dicing have high adhesive force and adhesion, water will flow toward the contact surfaces of these contact surfaces during dicing. Intrusion is inhibited. Furthermore, the adhesive force and adhesion between the hardened material 1320' and the semiconductor wafer 9' become higher. Therefore, in this step, peeling of a part or all of the cured product 1320' from the semiconductor wafer 9' is suppressed, and the transferability of the cured product 1320' to the semiconductor wafer 9' is high.

Here, the pickup direction is indicated by arrow I. The separation means 8 for separating the semiconductor wafer 9' from the support sheet 10 together with the cut first layer 131' and the cured product 1320' includes, for example, a vacuum collet. In addition, in FIG. 6, unlike the semiconductor wafer with the hardened die-bonding film, the separation means 8 is not shown in cross section.

Heretofore, the method of manufacturing a semiconductor wafer in the case of using the dicing die-bonding sheet 1A has been described, but the dicing die-bonding sheets 1B, 1C, 1D, etc., use other dicing wafers of the present invention other than the dicing die-bonding sheet 1A. In the case of the die-bonding sheet, even when the dicing die-bonding sheet 1A is not used at the initial stage and a die-bonding film is used, a semiconductor wafer can be produced by the same method as described above. Thus, the effect achieved in this case is also the same as in the case of using the dicing die-bonding sheet 1A. In the case of using other dicing die-bonding sheets, according to the structure, arbitrary steps can be appropriately added to manufacture a semiconductor wafer.

>>Semiconductor device and its manufacturing method>> The semiconductor wafer with the cured die-bonding film obtained by applying the above-mentioned manufacturing method (semiconductor wafer having the first layer after cutting and the second layer after cutting and curing) is particularly suitable for the manufacture of semiconductor devices. For example, the above-mentioned semiconductor wafer with the cured die-bonding film is die-bonded on the circuit formation surface of the substrate through the first layer after cutting. FIG. 7 is a cross-sectional view schematically showing an example of a state in which a semiconductor wafer with a hardened die-bonding film is bonded to the circuit formation surface of such a substrate. Here, the semiconductor wafer 9 ′ having the first layer 131 ′ after cutting and the cured product 1320 ′ described using the manufacturing method described with reference to FIG. 6 is shown as a semiconductor wafer with a cured die-bonding film. situation.

As shown in FIG. 7 , the semiconductor wafer 9 ′ with the cured die-bonding film 130 ′ has a die on the circuit formation surface 7 a of the substrate 7 through the first layer 131 ′ after cutting among the aforementioned films 130 ′. engage. More specifically, the surface 131b' on the opposite side of the first layer 131' after the cut to the side of the cured product 1320' (referred to as the "second surface" in this specification) 131b' is in direct contact with the circuit forming surface 7a of the substrate 7, The semiconductor wafer 9 ′ is fixed on the substrate 7 . In addition, description of the circuit in the board|substrate 7 is abbreviate|omitted.

The embeddedness of the substrate of the first layer 131 of the die-bonding thin film 13 described above is good. Therefore, as shown here, between the circuit formation surface 7a of the substrate 7 and the first layer 131' after cutting, the occurrence of gaps (holes) is suppressed, and the first layer 131' after cutting is well embedded in the circuit of the substrate 7 The surface 7a is formed and covered.

Here, the die bonding of the semiconductor wafer in the case of using the dicing die-bonding sheet 1A will be described, but the dicing die-bonding sheets 1B, 1C, or 1D, etc., use other aspects of the present invention other than the dicing die-bonding sheet 1A. In the case of dicing the die-bonding sheet, even if the die-bonding sheet 1A is not diced at the initial stage and the die-bonding thin film is used, the substrate is satisfactorily embedded through the first layer as described above.

As described above, a semiconductor package and a semiconductor device are manufactured by the same method as the conventional method using the semiconductor wafer with the hardened die-bonding film, after the semiconductor wafer is die-bonded. For example, if necessary, at least one semiconductor wafer is further laminated on the die-bonded semiconductor wafer, and after wire bonding is performed, all of the obtained semiconductor wafers are sealed with resin to produce a semiconductor package. Then, using this semiconductor package, a target semiconductor device is fabricated. By using the die-bonding film or the dicing die-bonding sheet of the present invention, the embedment of the substrate of the first layer is favorable, and as a result, the obtained semiconductor package has high reliability.

In another aspect, a die-bonding film according to an embodiment of the present invention includes a first layer and a second layer on top of the first layer; The first layer has the characteristic that the initial detection temperature of the melt viscosity is 50~75°C (may be 50~68°C or 50~59°C); The aforementioned second layer has adhesiveness and energy ray hardening properties; The aforementioned die-bonding films have the following characteristics: The laminate of the first and second layers with a thickness of 10 μm and a width of more than 25 mm was used as a test piece, the test piece was attached to a mirror-surface silicon wafer, the test piece was cut into a width of 25 mm, and the cut The test piece and the above-mentioned mirror-surface silicon wafer were left to stand for 30 minutes in a dark place in an air environment at a temperature of 23°C and a relative humidity of 50%, and the above-mentioned test piece after the stand-still preservation was cured by energy ray to become When the cured product is attached to the non-immersion test laminated body of the mirror-surface silicon wafer before the production, the adhesive force between the cured product with a width of 25mm and the mirror-surface silicon wafer is 6~20N/25mm or 10~20N/25mm.

In addition, the die bonding film may be such that: the first layer is formed of a first adhesive composition; the second layer is formed of a second adhesive composition; and the first adhesive composition may include a polymer Component (a), epoxy-based thermosetting resin (b) composed of epoxy resin (b1) and thermosetting agent (b2), curing accelerator (c), filler (d), and coupling agent ( e), the aforementioned polymer component (a) is the acrylic resin formed by the copolymerization of n-butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate, or n-butyl acrylate, acrylic acid The content of the acrylic resin (the polymer component (a)) obtained by copolymerizing ethyl ester, acrylonitrile, and glycidyl methacrylate, relative to the total mass of the first adhesive composition (excluding the solvent), 5 to 20 mass %, preferably 7 to 12 mass %); the aforementioned epoxy resin (b1) is a bisphenol A type epoxy resin and a polyfunctional aromatic type (triphenyl type) epoxy resin, or a bisphenol F-type epoxy resin and dicyclopentadiene-type epoxy resin; the above-mentioned thermosetting agent (b2) is an o-cresol type phenolic resin; (the content of the above-mentioned epoxy-based thermosetting resin (b) is relative to the above-mentioned polymerization The content of the component (a) is 800 to 1000 parts by mass, and the content of the aforementioned thermosetting agent (b2) is preferably 25 to 80 parts by mass relative to 100 parts by mass of the aforementioned epoxy resin (b1) content parts); the aforementioned hardening accelerator (c) is the inclusion of 1 molecule of 5-hydroxyisophthalic acid (HIPA) and 2 molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ). compound, or 2-phenyl-4,5-dihydroxymethylimidazole (the content of the above-mentioned curing accelerator (c) is preferably 100 parts by mass relative to the content of the above-mentioned epoxy-based thermosetting resin (b) 0.1~2 parts by mass); The filler (d) is spherical silica modified with epoxy groups (the content of the filler (d), relative to the total mass of the first adhesive composition (excluding the solvent), is preferably 15~ 30% by mass); The aforementioned coupling agent (e) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and oligomers having epoxy, methyl and methoxy groups The content of at least one of the polymer-type silane coupling agents (the coupling agent (e) is preferably 100 parts by mass relative to the total content of the polymer component (a) and the epoxy-based thermosetting resin (b) in 100 parts by mass. 0.1~5 parts by mass); The second adhesive composition includes a polymer component (a), a filler (d), a coupling agent (e), an energy ray thermosetting resin (g), and a photopolymerization initiator (h); The aforementioned polymer component (a) is an acrylic resin obtained by copolymerization of n-butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate, or n-butyl acrylate, ethyl acrylate, The content of the acrylic resin (the polymer component (a)) obtained by copolymerizing acrylonitrile and glycidyl methacrylate is preferably a content of the total mass (excluding the solvent) of the second adhesive composition. 20~35% by mass); The filler (d) is epoxy-modified spherical silica or silica filler (the content of the filler (d) is relative to the total mass of the second adhesive composition (excluding the solvent) , preferably 45 to 64 mass %); The coupling agent (e) is an oligomer type silane coupling agent having an epoxy group, a methyl group and a methoxy group (with respect to 100 parts by mass of the polymer component (a), preferably 0.1 to 5 parts by mass ); The aforementioned energy ray curable resin (g) is tricyclodecane dimethylol diacrylate or ε-caprolactone modified s-(2-acrylooxyethyl) isocyanate (the aforementioned energy ray curable resin) The content of (g) is preferably 5 to 85% by mass relative to the total mass of the second adhesive composition (excluding the solvent); The aforementioned photopolymerization initiator (h) is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (the aforementioned photopolymerization initiator (h) The content is 1 to 10 parts by mass relative to 100 parts by mass of the content of the energy ray-curable resin (g).

[Example] Hereinafter, the present invention will be described in more detail by means of specific embodiments. However, the present invention is not limited to the examples shown below.

>Single > The official names of the monomers abbreviated in the Examples and Comparative Examples are shown below. BA: n-butyl acrylate MA: methyl acrylate HEA: 2-hydroxyethyl acrylate GMA: Glycidyl Methacrylate EA: Ethyl Acrylate AN: Acrylonitrile

>Manufacturing raw materials of adhesive composition> The raw materials used for the production of the adhesive compositions in the present examples and comparative examples are shown below.

[Polymer component (a)] (a)-1: Acrylic resin (weight average molecular weight 500000, glass transfer temperature -1°C). (a)-2: Acrylic resin (weight average molecular weight 700,000, glass transfer temperature 10°C). (a)-3: Acrylic resin (weight average molecular weight 800,000, glass transfer temperature -30°C). (a)-4: Thermoplastic resin, polyester (“VYLON 220” manufactured by Toyobo Co., Ltd., weight average molecular weight 35,000, glass transition temperature 53°C) [Epoxy resin (b1)] (b1)-1: Bisphenol A epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184~194g/eq) (b1)-2: Polyfunctional aromatic type (triphenyl type) epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 167 g/eq, softening point 54°C, weight average molecular weight 1200) (b1)-3: Bisphenol F-type epoxy resin (“YL983U” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 170 g/eq) (b1)-4: Dicyclopentadiene-type epoxy resin (“XD-1000-L” manufactured by Nippon Kayakuyo Co., Ltd., epoxy equivalent: 248 g/eq) (b1)-5: Mixture of liquid bisphenol A epoxy resin and acrylic rubber fine particles (“BPA328” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 235 g/eq) (b1)-6: Dicyclopentadiene type epoxy resin (“EPICLON HP-7200HH” manufactured by DIC Corporation, epoxy equivalent weight 255~260g/eq) [Thermosetting agent (b2)] (b2)-1: o-cresol-type phenolic resin (“PHENOLITE KA-1160” manufactured by DIC Corporation) (b2)-2: Novolac type phenol resin (phenol resin other than o-cresol type, "BRG-556" manufactured by Showa Denko Corporation) (b2)-3: Dicyandiamide (“ADEKA HARDENER EH-3636AS” manufactured by ADEKA, solid dispersion type latent hardener, active hydrogen content 21 g/eq) [Hardening accelerator (c)] (c)-1: Inclusion compound of 1 molecule of 5-hydroxyisophthalic acid (HIPA) and 2 molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) (Japan Soda Co., Ltd. "HIPA-2P4MHZ") (c)-2: 2-Phenyl-4,5-dihydroxymethylimidazole (“CUREZOL 2PHZ-PW” manufactured by Shikoku Chemical Industry Co., Ltd.) [filler (d)] (d)-1: Spherical silica modified with epoxy group (“ADMANANO YA050C-MKK” manufactured by ADMATECHS, average particle size 50 nm) (d)-2: Silica filler (“SC2050MA” manufactured by ADMATECHS, surface-modified silica filler with epoxy compound, average particle size 500nm) [Couplant (e)] (e)-1: 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu SILICON Co., Ltd., silane coupling agent, methoxyl equivalent 12.7 mmol/g, molecular weight 236.3) (e)-2: 3-glycidoxypropyltriethoxysilane ("KBE-403" manufactured by Shin-Etsu SILICON Co., Ltd., silane coupling agent, methoxyl equivalent 8.1 mmol/g, molecular weight 278.4) (e)-3: Oligomer-type silane coupling agent having epoxy group, methyl group and methoxy group (“X-41-1056” manufactured by Shin-Etsu SILICON Co., Ltd., epoxy equivalent weight: 280 g/eq) (e)-4: Trimethoxy[3-(phenylamino)propyl]silane (“SZ6083” manufactured by DOW CORNING TORAY, silane coupling agent) (e)-5: 3-glycidoxypropyltrimethoxysilane-added silicate compound (“MKC SILICATE MSEP2” manufactured by Mitsubishi Chemical Corporation) [Crosslinking agent (f)] (f)-1: Toluene diisocyanate trimer adduct of trimethylolpropane (“BHS8515” manufactured by TOYOCHEM) [Energy beam curable resin (g)] (g)-1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., UV-curable resin, molecular weight 304) (g)-2: ε-Caprolactone-modified gins-(2-acrylooxyethyl) isocyanurate (“A-9300-1CL” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional ultraviolet light compound) [Polymerization initiator (h)] (h)-1: 1-Hydroxycyclohexyl phenone (“IRGACURE (registered trademark) 184” manufactured by BASF) (h)-2: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE (registered trademark) 369” manufactured by BASF)

[Example 1] >>Manufacture of Die Bonding Film>> >Manufacture of 1st Adhesive Composition> Polymer component (a)-1 (10 parts by mass), epoxy resin (b1)-1 (20 parts by mass), epoxy resin (b1)-2 (25 parts by mass), thermosetting agent (b2)- 1 (25 parts by mass), hardening accelerator (c)-1 (0.3 parts by mass), filler (d)-1 (20 parts by mass), coupling agent (e)-1 (0.3 parts by mass), coupling agent ( e)-2 (0.4 mass part) and coupling agent (e)-3 (0.5 mass part) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23° C. to obtain a first adhesive composition with a solid concentration of 55 mass %. In addition, all the compounding amounts of components other than methyl ethyl ketone shown here are solid content conversion values.

>Manufacture of 2nd Adhesive Composition> Polymer component (a)-1 (22 parts by mass), filler (d)-2 (50 parts by mass), coupling agent (e)-3 (0.5 parts by mass), energy ray thermosetting resin (g) -1 (20 parts by mass) and photopolymerization initiator (h)-2 (0.3 parts by mass) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to obtain a second adhesive composition with a solid concentration of 55% by mass . In addition, the compounding quantities of components other than methyl ethyl ketone shown here are all solid content conversion values.

> Formation of Layer 1 > A release film (“SP-PET381031H” manufactured by LINTECH Co., Ltd., thickness 38 μm) in which one side of a film made of polyethylene terephthalate (PET) was treated with silicone to be peeled off was used. 1. The adhesive composition was heated and dried at 100° C. for 2 minutes to form a first layer with a thickness of 10 μm.

> Formation of Layer 2 > A release film (“SP-PET381031H” manufactured by LINTECH Co., Ltd., thickness 38 μm) in which one side of a film made of polyethylene terephthalate (PET) was treated with silicone to be peeled off was used. 2. The adhesive composition was heated and dried at 100° C. for 2 minutes to form a second layer with a thickness of 10 μm.

>Manufacture of Die Bonding Films> The exposed surface on the opposite side of the release film side of the first layer obtained above and the exposed surface on the opposite side of the release film side of the second layer obtained above were bonded together by making the temperature of the two layers 40°C. , a release film, a first layer, a second layer, and a release film were sequentially laminated in these thickness directions to obtain a composed die-bonding film with a release film.

>>Manufacture of Die Bonding Sheets>> The release film on the side of the first layer was removed from the die-bonding film obtained above, and the exposed surface of the first layer thus newly generated was bonded to the substrate to obtain a substrate, a first layer, A dicing die-bonding sheet composed of a second layer and a release film (in other words, a base material, a die-bonding film, and a release film). The base material used here was a polyethylene film (thickness 100 μm).

>>Evaluation of the die-bonding film>>>Calculation of initial detection temperature T ₀ of melt viscosity> The first layer of the die-bonding film obtained above was laminated, and a cylindrical test piece with a diameter of 10 mm and a height of 20 mm was directly produced. The produced test piece was immediately placed at the measurement position of a capillary rheometer (“CFT-100D” manufactured by Shimadzu Corporation), and a force of 5.10 N (50 kgf) was applied to the test piece, and the test piece was heated at a rate of 10°C/ min, the temperature was raised from 50°C to 120°C. Then, when the test piece was extruded from a hole of 0.5 mm in diameter and 1.0 mm in height provided in the crystal grain, that is, the temperature at which the test piece started to detect the melt viscosity (initial detection temperature T ₀ ) (°C) was obtained. The results are shown in Table 1.

>Evaluation of Embedding Properties of Substrates> (Manufacture of Semiconductor Wafers with Hardened Die Bonding Films) The peeling film was removed from the dicing die-bonding sheet obtained above, and the exposed surface of the newly generated second layer (die-bonding film) was attached to the mirror surface (back surface) of an 8-inch mirror-surface silicon wafer (thickness 350 μm). At this time, the dicing die-bonding sheet was heated to 40° C., attached at a speed of 20 mm/s, and attached at a pressure of 0.5 MPa. As a result of the above, a build-up layer consisting of a base material, a first layer, a second layer, and a mirror-surface silicon wafer (in other words, a base material, a die-bonding film, and a mirror-surface silicon wafer) can be obtained by laminating the base material, the first layer, the second layer, and the mirror-surface silicon wafer in this order in the thickness direction. body (1).

Then, by dicing using a dicing device (“DFD6361” manufactured by Disco Corporation), the mirror-surface silicon wafer in the laminated body (1) is divided, and the first and second layers (die-bonding films) are also cut at the same time. A silicon wafer with a size of 2mm×2mm was obtained. The dicing at this time was performed with the moving speed of the dicing blade at 30 mm/sec and the number of rotations of the dicing blade at 40,000 rpm, and the substrate was cut to a depth of 20 μm with the dicing blade from the adhesive surface of the first layer. In addition, dicing is performed while running water (dicing water) at the contact position of the dicing blade with the mirror-surface silicon wafer. By the above, the first layer after cutting, the second layer after cutting, and the silicon wafer (mirror-surface silicon wafer after cutting) (in other words, the cutting die-bonding film) can be obtained by stacking these layers in the thickness direction in this order. and a silicon wafer) a plurality of laminates, through the first layer, to obtain a laminate (2) fixed in an aligned state on the substrate.

Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH), under the conditions of an illuminance of 220 mW/cm ² and an amount of light of 120 mJ/cm ² , from the outside of the base material side of the laminate (2), the The second layer after cutting in the layered body (2) is irradiated with ultraviolet rays to cure the second layer. By the above, a plurality of laminates of the first layer after cutting, the cured product of the second layer after cutting, and the silicon wafer can be laminated in this order in the thickness direction. A laminated body (3) in a fixed state. The layered body (3) is the same as the layered body (2) except that the second layer is cured after cutting.

Next, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by CANON MACHINERY), the first layer on the back surface and the cured second layer (cured second layer) were separated from the base material in the laminate (3) obtained above Die-bonding film) silicon wafers (ie, silicon wafers with hardened die-bonding films) are picked up. By the above, the silicon wafer with the hardened die-bonding film is obtained.

Table 1 shows the order of the dicing (cutting of the die-bonding film), curing of the die-bonding film (second layer), and pick-up up to this point. In addition, the order of carrying out the three steps described above is not limited to the evaluation in this item (embeddability of the substrate), and the same applies to the evaluation of other items described later. The symbols in Table 1 have the following meanings. DF: Die Bonding Film DC: cut PU: pick up

(Evaluation of Embedding Properties of Die Bonding Films in Substrates) A disk-shaped transparent glass substrate (manufactured by N SG PRECISION, 8 inches in diameter, 100 μm in thickness) was divided into a size of 8 mm×8 mm and separated into pieces. Next, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by CANON MACHINERY), the silicon wafer with the cured die bonding film obtained above was die bonded to the singulated transparent substrate obtained above. At this time, at a temperature of 20°C, the singulated transparent glass substrate is in contact with the hardened die-bonding film, and the silicon wafer with the hardened die-bonding film is placed on the substrate. Die-bonding was performed by applying a force of 5 N for 0.5 seconds to one silicon wafer with a hardened die-bonding film.

Next, using an optical microscope ("VHX-1000" manufactured by KEYENCE Corporation), the transparent glass substrate after die bonding was observed from the side opposite to the side of the hardened die bonding film. After that, the presence or absence of voids (voids) between the hardened die-bonding film and the glass substrate was confirmed, and the entire surface of the glass substrate on the side of the hardened die-bonding film and the hardened die-bonding film were obtained. The ratio of the surfaces that are close together (adhesion ratio, area %).

The above operation was performed on 9 silicon wafers with hardened die-bonding films, and the embedding properties of the substrates of the die-bonding films were evaluated according to the following criteria. The results are shown in Table 1. A: In all of the nine silicon wafers with hardened die-bonding films, the adhesion ratio was 90 area % or more. B: At least one silicon wafer with the hardened die-bonding film with the aforementioned adhesion ratio of less than 90 area % exists.

>Evaluation of transferability of semiconductor wafers> (Manufacture of Laminate (3)) The laminate ( 3 ) is produced in the same manner as in the production of the above-described semiconductor wafer with the hardened die-bonding film.

(Evaluation of Transferability to Semiconductor Wafers) Next, the layered body (3) obtained above was immersed in pure water at 23°C for 2 hours. At this time, the entire layered body (3) is immersed in pure water to arrange the layered body (3). Next, the layered body (3) was taken out from pure water, and the water droplets adhering to the surface were removed. Then, using a pick-up and die-bonding device (“BESTEM D02” manufactured by CANON MACHINERY), the base material in the layered body (3) after dipping was tested, and the first layer and the hardened second layer on the back surface were separated and picked up. A silicon wafer (in other words, a silicon wafer with a hardened die-bonding film). The procedure of dicing, curing of the die-bonding film (second layer), and pick-up up to this point is the same as the evaluation of the embedding property of the above-mentioned die-bonding film in the substrate.

Next, using an optical microscope (“VHX-1000” manufactured by KEYENCE Corporation), the surface (in other words, the first surface) on which the first layer (die-bonding film) of the base material is laminated was observed, and the hardened crystals were evaluated according to the following criteria. Transferability of particle bonding films to semiconductor wafers. The results are shown in Table 1. A: The hardened die-bonding film does not remain on the base material. B: The hardened die-bonding film (at least the first layer) remains on the base material.

>Determination of non-dipping adhesion and post-dipping adhesion> (Manufacture of laminated body for testing) The release film on the second layer side was removed from the die-bonding film obtained above, and the exposed surface of the newly generated second layer was attached to the mirror surface (back surface) of a 6-inch mirror-surface silicon wafer (thickness 350 μm). At this time, the die-bonding film was heated to 40° C., and adhered on the conditions of an attaching speed of 20 mm/s and an attaching pressure of 0.5 MPa. Next, the peeling film on the first layer side was removed from the attached die-bonding film, and the exposed surface of the newly generated first layer was attached to a strong adhesive tape (“PET50PLsin” manufactured by Lintech Corporation) with a width of 25 mm.

Next, for the die-bonding film attached to the aforementioned 6-inch mirror-surface silicon wafer, along the periphery of the strong adhesive tape, the entire area in the thickness direction of the aforementioned die-bonding film (the first and second layers) The entire area in the thickness direction) was formed with a notch, and the above-mentioned die-bonding film was cut into a strip having a width of 25 mm. Next, immediately after the aforementioned cutting, the cut die-bonding film and the aforementioned mirror-surface silicon wafer were immersed in pure water at 23° C. for 2 hours in a dark place. At this time, the mirror-surface silicon wafer to which the cut die-bonding film is attached is placed in pure water in a state where the entirety is immersed in pure water. Next, the mirror-surface silicon wafer to which the cut die-bonding film is attached is taken out of pure water, and the water droplets adhering to the surface are removed. Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH Co., Ltd.), under the conditions of an illuminance of 220 mW/cm ² and a light intensity of 120 mJ/cm ² , ultraviolet rays were irradiated to the die-bonding film after cutting, so that the second layer hardening. As a result, a laminated body for testing in which the strong adhesive tape, the first layer for forming a score, the cured product for the second layer for forming a score, and a mirror-surface silicon wafer are laminated in this order in the thickness direction can be obtained.

(Measurement of Post-Dipping Adhesion of Test Laminates) The strong adhesive tape in the test laminate obtained above was stretched under the condition of 23° C. using a universal tensile tester (“AUTOGRAPH AG-IS” manufactured by Shimadzu Corporation). At this time, the strong adhesive tape was stretched at a peeling (stretching) speed of 300 mm/min so that the peeling surfaces generated in the laminate for testing formed an angle of 180° with each other, and a so-called 180-degree process was performed. ° Peel. After that, the peeling force (load, N/25 mm) at this time was measured, and the peeling position and peeling form that occurred in the test laminate were confirmed. Then, the said peeling force is the adhesive force (N/25mm) between the hardened|cured material of the 2nd layer of width 25mm in the laminated body for a test, and a mirror surface silicon wafer. The results are shown in the column of "Adhesion after immersion" in Table 1.

(Manufacture of laminated body for non-immersion test) Except that the mirror-surface silicon wafer to which the die-bonding film after cutting is attached is left to stand for 30 minutes at a temperature of 23°C and a relative humidity of 50% in a dark place in an air environment, instead of pure pure water at 23°C in a dark place. Except for the step of immersion in water for 2 hours, a non-immersion test layered body was produced by the same method as in the case of the above-mentioned test layered body.

(Measurement of non-immersion adhesive force of laminate for non-immersion test) The peeling force (load, N/25 mm) of the obtained non-immersion test layered body was measured in the same manner as in the case of the above-mentioned test layered body, and the peeling position and For the peeling form, the aforementioned peeling force was defined as the adhesive force (N/25mm) between the cured object of the second layer with a width of 25mm and the mirror-surface silicon wafer. The results are shown in the column of "non-dipping adhesion" in Table 1.

>>Manufacture of die-bonding films, manufacture of diced die-bonding sheets, and evaluation of die-bonding films>> [Example 2] For the first adhesive composition and the second adhesive composition, the types and contents of the components contained in these compositions are as shown in Table 1. In the same manner as in the case of Example 1, a die-bonding film and a dicing die-bonding sheet were produced, and the die-bonding film was evaluated. The results are shown in Table 1.

[Comparative Example 1] >>Manufacture of die-bonding films, manufacture of diced die-bonding sheets>> In the same manner as in the case of Example 1, a die-bonding film and a dicing die-bonding sheet were produced.

>>Evaluation of Die Bonding Film>>>Calculation of Initial Detection Temperature T ₀ of Melt Viscosity> The initial detection temperature T ₀ (° C.) was obtained by the same method as in Example 1. The results are shown in Table 2.

>Evaluation of Embedding Properties of Substrates> (Manufacture of semiconductor wafer with hardened die-bonding film for comparison) A layered body (1) was produced in the same manner as in the case of Example 1.

Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH Co., Ltd.), under the conditions of an illuminance of 220 mW/cm ² and a light intensity of 120 mJ/cm ² , from the outside of the base material side of the laminate (1), the The second layer in the layered body (1) is irradiated with ultraviolet rays to cure the second layer. As a result of the above, a laminate (4) in which the cured product of the first layer, the second layer, and the mirror-surface silicon wafer are laminated in this order in the thickness direction can be obtained. The layered body (4) is the same as the layered body (1) except that the second layer is hardened.

Next, by dicing using a dicing device (“DFD6361” manufactured by Disco), the mirror-surface silicon wafer in the laminate (4) is divided, and the first layer and the cured second layer (cured) are also cut at the same time. Die bonding film) to obtain a silicon wafer with a size of 2 mm x 2 mm. The dicing at this time was performed with the moving speed of the dicing blade at 30 mm/sec and the number of rotations of the dicing blade at 40,000 rpm, and the substrate was cut to a depth of 20 μm with the dicing blade from the adhesive surface of the first layer. By the above, it is possible to obtain a plurality of laminates consisting of the first layer after cutting, the cured second layer after cutting, and the silicon wafer in this order in the thickness direction. The above laminated body (3') for comparison is fixed in the state of alignment. In the laminated body (3') for comparison, the appearance of each layer and the order of lamination are the same as in the case of the above-mentioned laminated body (3), but the order of cutting and curing of the second layer is the same as the above-mentioned laminated body (3) situation is different.

Next, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by CANON MACHINERY Co., Ltd.), the base material in the laminated body for comparison (3') obtained above was tested, and the first layer having the first layer and the cured second layer on the back surface were separated. The silicon wafer of the layer (hardened die-bonding film) (in other words, the silicon wafer with the comparative hardened die-bonding film) is picked up. Through the above, a silicon wafer with a hardened die-bonding film for comparison was obtained.

(Evaluation of Embedding Properties of Die Bonding Films in Substrates) The embeddability of the substrate with the hardened die-bonding film was evaluated in the same manner as in the case of Example 1, except that the obtained silicon wafer with the hardened die-bonding film for comparison was used. The results are shown in Table 2.

>Evaluation of transferability of semiconductor wafers> (Manufacture of laminated body (3') for comparison) A laminated body (3') for comparison was produced in the same manner as in the production of the semiconductor wafer with the cured die-bonding thin film for comparison.

(Evaluation of Transferability to Semiconductor Wafers) Next, the laminated body (3') for comparison obtained above was immersed in pure water at 23°C for 2 hours. At this time, the laminated body (3') for comparison was arranged in a state where the whole of the laminated body (3') for comparison was immersed in pure water. Next, the laminated body (3') for comparison was taken out from pure water, and the water droplets adhering to the surface were removed. Then, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by CANON MACHINERY), the base material in the comparative laminate (3') after immersion was tested, and the first layer on the backside and the hardened second layer were separated. Two-layer silicon wafers (in other words, silicon wafers with hardened die-bonding films for comparison) were picked up. Next, the transferability of the hardened die-bonding film to the semiconductor wafer was evaluated in the same manner as in Example 1, except that the obtained silicon wafer with the hardened die-bonding film for comparison was used. . The results are shown in Table 2.

>Measurement of Non-Dipping Adhesion and Post-Dipping Adhesion> (Manufacture of Test Laminate) In the same manner as in Example 1, a mirror-surface silicon wafer to which the cut die-bonding film was attached was obtained. Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH Co., Ltd.), under the conditions of an illuminance of 220 mW/cm ² and a light intensity of 120 mJ/cm ² , ultraviolet rays were irradiated to the die-bonding film after cutting, so that the second layer hardening. Next, the second-layer hardened die-bonding film was immersed in pure water at 23° C. for 2 hours with the mirror-surface silicon wafer immediately after the second-layer hardening in a dark place. At this time, the mirror-surface silicon wafer to which the hardened die-bonding film is attached is placed in pure water in a state of being completely immersed in pure water. Next, the mirror-surface silicon wafer to which the hardened die-bonding film is attached is taken out of pure water, and the water droplets adhering to the surface are removed. As a result of the above, a laminated body for comparison, which consists of a strong adhesive tape, a first layer for forming a score, a cured product for forming a second layer for forming a score, and a mirror-surface silicon wafer, are sequentially laminated in the thickness direction. .

(Manufacture of laminated body for non-immersion test) Except that the mirror-surface silicon wafer with the hardened die-bonding film attached to the second layer was left for 30 minutes in a dark place in an air environment at a temperature of 23°C and a relative humidity of 50% for 30 minutes, instead of being stored in a dark place for 23 minutes A non-immersion test layered body for comparison was produced by the same method as in the case of the above-mentioned comparison layered body for testing, except for the step of immersing in pure water at a temperature of C for 2 hours.

(Measurement of non-dipping adhesive force and post-dipping adhesive force of test laminate) The adhesive force after immersion was measured by the same method as in the case of Example 1 using the laminate for comparison obtained above. Moreover, the non-immersion adhesive force was measured by the same method as the case of Example 1 using the laminated body for the non-immersion test for comparison obtained above. The results are shown in Table 2.

>>Manufacture of die-bonding films, manufacture of diced die-bonding sheets, and evaluation of die-bonding films>> [Comparative Example 2] >>Manufacture of die-bonding films, manufacture of diced die-bonding sheets, and evaluation of die-bonding films>> Except that the die-bonding film and the dicing die-bonding sheet were produced in the same manner as in the case of Example 2, instead of the die-bonding film and the dicing die-bonding sheet produced in the same manner as in the case of Example 1 Otherwise, the same method as in the case of Comparative Example 1 was used to evaluate the die-bonding thin film. The results are shown in Table 2.

[Comparative Example 3] >>Manufacture of Die Bonding Film>> >Manufacture of adhesive composition> Polymer component (a)-3 (10 parts by mass), polymer component (a)-4 (20 parts by mass), epoxy resin (b1)-2 (20 parts by mass), epoxy resin (b1)- 5 (20 parts by mass), thermosetting agent (b2)-2 (20 parts by mass), hardening accelerator (c)-2 (0.3 parts by mass), filler (d)-2 (10 parts by mass), coupling agent (e)-4 (0.3 parts by mass), coupling agent (e)-5 (0.5 parts by mass), energy ray-curable resin (g)-1 (5 parts by mass), and photopolymerization initiator (h)- 1 (0.15 parts by mass) was dissolved or dispersed in methyl ethyl ketone, and stirred at 23° C. to obtain an adhesive composition having a solid content concentration of 55% by mass. In addition, the compounding quantities of components other than methyl ethyl ketone shown here are all solid content conversion values.

>Manufacture of Die Bonding Films> A release film (“SP-PET381031H” manufactured by LINTECH, thickness 38 μm) in which one side of a film made of polyethylene terephthalate (PET) was treated with silicone to be peeled off was used, and applied to the peeled side of the film. The above-obtained adhesive composition was heated and dried at 100° C. for 2 minutes to form a 20 μm-thick die-bonding thin film.

>>Manufacture of Die Bonding Sheets>> By bonding the exposed surface of the above-obtained die-bonding film to the base material, a dicing die-bonding sheet formed by laminating the base material, the die-bonding film, and the release film in this order in the thickness direction is obtained. The substrate used here is the same as that used in Example 1.

>>Evaluation of the die-bonding film>>>Calculation of the initial detection temperature T ₀ of the melt viscosity> For the die-bonding film obtained above, the initial detection temperature T was obtained by the same method as in the case of Example 1 ₀ (°C). The results are shown in Table 2.

>Evaluation of Embedding Properties of Substrates> (Manufacture of semiconductor wafer with hardened die-bonding film for comparison) The peeling film was removed from the dicing die-bonding sheet obtained above, and the exposed surface of the newly generated die-bonding film was attached to the mirror surface (back surface) of an 8-inch mirror-surface silicon wafer (thickness 350 μm). At this time, the dicing die-bonding sheet was heated to 40° C., attached at a speed of 20 mm/s, and attached at a pressure of 0.5 MPa. As a result of the above, a laminate ( 5 ) in which the base material, the die-bonding film, and the mirror-surface silicon wafer are laminated in this order in the thickness direction can be obtained.

Next, by dicing using a dicing device (“DFD6361” manufactured by Disco), the mirror-surface silicon wafer in the laminate (5) is divided, and the die-bonding film is also cut to obtain a silicon wafer with a size of 2 mm×2 mm. . The dicing at this time was performed by cutting the substrate with the dicing blade from the adhered surface of the die-bonding film to a depth of 20 μm with the movement speed of the dicing blade at 30 mm/sec and the number of rotations of the dicing blade at 40,000 rpm. In this way, a plurality of laminates consisting of the cut die-bonding films and silicon wafers can be obtained in order in the thickness direction, and a laminate ( 6).

Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH), under the conditions of an illuminance of 220 mW/cm ² and a light intensity of 120 mJ/cm ² , from the outside of the base material side of the laminate (6), the The cut die-bonding thin film in the layered body (6) is irradiated with ultraviolet rays to harden the die-bonding thin film. By the above, it is possible to obtain the cured product of the cut die-bonding film and a plurality of stacked products of silicon wafers in order in the thickness direction, and to obtain a stacked layer fixed in an aligned state on the substrate through the cured product. body (7). The layered body (7) is the same as the layered body (6) except that the die-bonding thin film after cutting is cured.

Next, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by CANON MACHINERY), the silicon wafer having the hardened die bonding film on the back surface (ie, A comparative silicon wafer with a hardened die-bonding film) was picked up. From the above, a silicon wafer with a hardened die-bonding film for comparison was obtained.

(Evaluation of Embedding Properties of Die Bonding Films in Substrates) The embeddability of the substrate with the hardened die-bonding film was evaluated in the same manner as in the case of Example 1, except that the obtained silicon wafer with the hardened die-bonding film for comparison was used. The results are shown in Table 2.

>Evaluation of transferability of semiconductor wafers> (Production of Laminate (7)) A laminate (7) was produced in the same manner as in the case of producing the semiconductor wafer with the hardened die-bonding thin film for comparison.

(Evaluation of Transferability to Semiconductor Wafers) Next, the laminate (7) obtained above was immersed in pure water at 23°C for 2 hours. At this time, the layered body (7) is placed in a state where the entire layered body (7) is immersed in pure water. Next, the layered body (7) was taken out from pure water, and the water droplets adhering to the surface were removed. Then, using a pick-up and die-bonding device (“BESTEM D02” manufactured by CANON MACHINERY), the substrate in the layered body (7) after dipping was tested, and the silicon wafer with the hardened die-bonding film on the backside (in other words, the silicon wafer) was separated. , a comparative silicon wafer with hardened die-bonding film) was picked up. Thereafter, the transferability of the cured die-bonding film to the semiconductor wafer was evaluated in the same manner as in Example 1, except that the silicon wafer with the cured die-bonding film for comparison obtained above was used. . The results are shown in Table 2.

>Determination of non-dipping adhesion and post-dipping adhesion> (Manufacture of laminated body for testing) The exposed surface of the die-bonding film obtained above was attached to the mirror surface (back surface) of a 6-inch mirror-surface silicon wafer (thickness 350 μm). At this time, the die-bonding film was attached under the conditions of heating to 40° C., an attaching speed of 20 mm/s, and an attaching pressure of 0.5 MPa. Next, the peeling film was removed from the attached die-bonding film, and the exposed surface of the newly generated die-bonding film was attached to a strong adhesive tape (“PET50PLsin” manufactured by Lintech Corporation) with a width of 25 mm.

Next, for the die-bonding film attached to the 6-inch mirror-surface silicon wafer, along the periphery of the strong adhesive tape, a notch is formed in the entire area of the die-bonding film in the thickness direction, and the die-bonding film is attached. Cut into strips with a width of 25mm. Next, the cut die-bonding film was immersed in pure water at 23° C. for 2 hours with the mirror-surface silicon wafer immediately after cutting in a dark place. At this time, the mirror-surface silicon wafer to which the cut die-bonding film is attached is placed in pure water in a state of being completely immersed in pure water. Next, the mirror-surface silicon wafer to which the cut die-bonding film is attached is taken out of pure water, and the water droplets adhering to the surface are removed. Next, using an ultraviolet irradiation device (“RAD-2000 m/12” manufactured by LINTECH), under the conditions of an illuminance of 220 mW/cm ² and a light intensity of 120 mJ/cm ² , the cut die-bonding film was irradiated with ultraviolet rays to irradiate the die-bonding film. The bonding film hardens. As a result of the above, a laminated body for comparison, which consists of a strong adhesive tape, a cured product of a die-bonding film formed with a notch, and a mirror-surface silicon wafer, are laminated in this order in the thickness direction.

(Measurement of Post-Dipping Adhesion of Test Laminates) Under the condition of 23° C., using a universal tensile tester (“AUTOGRAPH AG-IS” manufactured by Shimadzu Corporation), the aforementioned strong adhesive tape in the aforementioned test laminate was stretched. At this time, the adhesive tape was stretched at a peeling (stretching) speed of 300 mm/min so that the peeling surfaces generated in the above-mentioned test layered body formed an angle of 180° by stretching the strong adhesive tape, and a so-called 180° ° Peel. After that, the peeling force (load, N/25 mm) at this time was measured, and the peeling position and peeling form that occurred in the laminate for the test were confirmed. Then, the said peeling force was used as the adhesive force (N/25mm) between the hardened|cured material of the die-bonding film of width 25mm and the mirror surface silicon wafer in the said laminated body for tests. The results are shown in the column "Adhesion after immersion" in Table 2.

(Manufacture of laminated body for non-immersion test) Except that the mirror-surface silicon wafer to which the die-bonding film after cutting is attached is left to stand for 30 minutes at a temperature of 23°C and a relative humidity of 50% in a dark place in an air environment, instead of pure pure water at 23°C in a dark place. Except for the step of immersing in water for 2 hours, a non-immersion test layered body for comparison was produced by the same method as in the case of the above-mentioned comparison layered body for testing.

(Measurement of non-immersion adhesive force of laminate for non-immersion test) The peeling force (load, N/25 mm) of the obtained non-immersion test layered product was measured in the same manner as in the case of the above-mentioned test layered product, and the peeling position generated in the non-immersion test layered product was confirmed. And peeling form, the said peeling force was used as the adhesive force (N/25mm) between the hardened|cured material of the second layer with a width of 25mm and the mirror-surface silicon wafer. The results are shown in the column of "non-dipping adhesion" in Table 2.

[Comparative Example 4] >>Manufacture of Die Bonding Film>> >Manufacture of adhesive composition> Polymer component (a)-3 (10 parts by mass), epoxy resin (b1)-4 (10 parts by mass), epoxy resin (b1)-5 (10 parts by mass), epoxy resin (b1)- 6 (20 parts by mass), thermosetting agent (b2)-3 (1 part by mass), hardening accelerator (c)-2 (1 part by mass), filler (d)-2 (50 parts by mass), coupling agent (e)-5 (0.5 parts by mass), crosslinking agent (f)-1 (0.3 parts by mass), energy ray curable resin (g)-1 (5 parts by mass), and photopolymerization initiator (h) -1 (0.15 parts by mass) was dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to obtain an adhesive composition with a solid concentration of 55 mass %. In addition, the compounding quantities of components other than methyl ethyl ketone shown here are all solid content conversion values.

>Manufacture of Die Bonding Films> A die-bonding thin film was produced in the same manner as in the case of Comparative Example 3, except that the adhesive composition obtained above was used.

>>Manufacture of dicing die-bonding sheets and evaluation of die-bonding films>> A dicing die-bonding sheet was produced and the die-bonding film was evaluated in the same manner as in the case of Comparative Example 3, except that the die-bonding film obtained above was used. The results are shown in Table 2.

[Table 1]

[Table 2]

As apparent from the above results, in Examples 1 to 2, among the die-bonding films, the initial detection temperature T ₀ of the first layer was 68° C. or lower (59 to 68° C.), and the first layer had an excellent substrate. burial.

Moreover, in Examples 1-2, the adhesive force after immersion between the cured object of the second layer and the mirror-surface silicon wafer was 10N/25mm or more (10N/25mm≦). In the measurement of the adhesive force after dipping, in the test laminate, peeling (interface peeling) occurred first between the first layer and the strong adhesive tape, and the peeling force at this time was 10N/25mm, and the second layer No debonding occurred between the hardened object and the mirrored silicon wafer. In addition, the non-immersion adhesive force between the cured object of the second layer and the mirror-surface silicon wafer is the same as the adhesive force after immersion, which is 10N/25mm or more. body), no peeling occurred between the second layer hardened object and the mirror-surface silicon wafer. Thus, the second-layer hardened die-bonding film is excellent in transferability to the semiconductor wafer.

As described above, since the die-bonding films of Examples 1 and 2 have a two-layer structure, when a semiconductor wafer of small size is picked up, the transfer defect to the semiconductor wafer can be suppressed, and the substrate can be buried well during the die-bonding process. enter.

In contrast to these, in Comparative Examples 1 and 2, the post-immersion adhesive force between the cured object of the second layer and the mirror-surface silicon wafer was as small as 3.0 N/25 mm or less (2.3 to 3.0 N/25 mm). At this time, in the test laminate for comparison, peeling (interfacial peeling) occurred between the cured object of the second layer and the mirror-surface silicon wafer. In addition, the non-dipping adhesive force between the cured object of the second layer and the mirror-surface silicon wafer was 10 N/25 mm or more, as in the cases of Examples 1 and 2. Therefore, the transferability to the semiconductor of the hardened second-layer die-bonding film is poor.

Comparative Example 1, Example 1, Comparative Example 2 and Example 2 are the same in the die-bonding film and the dicing die-bonding sheet, respectively. However, the reason for such a result is that in the evaluation, the procedure of immersion in pure water and curing (curing of the second layer) of the die-bonding film after the cutting of the attached mirror-surface silicon wafer was performed in Example 1. ~2 and Comparative Examples 1 to 2 are the opposite. In the case of Examples 1 to 2, the cut die-bonding films were immersed in pure water and then hardened. Considering that dicing using a dicing blade is performed together with running water (cutting water), the evaluations in Examples 1 to 2 can be said to reflect the order of steps for curing the die-bonding film after dicing. On the other hand, in the case of Comparative Examples 1 to 2, the die-bonding film after cutting was immersed in pure water after curing. That is, in the evaluation of Comparative Examples 1 and 2, it can be said that the order of steps in which the die-bonding film is hardened and then diced is reflected. Therefore, the evaluation results of these Examples and Comparative Examples show that, using the die-bonding film of the present invention, by following the above-mentioned production steps of the layered body (1), the production process of the layered body (2), and the layered body (3) The manufacturing step and the picking-up step are performed in this order, and when a semiconductor wafer with a small size is picked up, the transfer defect of the die-bonding film to the semiconductor wafer can be suppressed, and the semiconductor wafer can be manufactured at the same time.

In addition, in Comparative Example 3, the die-bonding film has a single-layer structure, and the adhesive force after immersion between the cured product of the die-bonding film and the mirror-surface silicon wafer is as small as 3.1 N/25 mm. At this time, in the laminated body for the test, peeling (interface peeling) occurred between the cured product of the die-bonding film and the mirror-surface silicon wafer. In addition, the non-dipping adhesive force between the hardened object of the die bonding film and the mirror-surface silicon wafer was 10 N/25 mm or more, as in the cases of Examples 1 to 2. Then, the transferability of the hardened|cured material of a die-bonding film to a semiconductor wafer is inferior.

On the other hand, in Comparative Example 4, the initial detection temperature T ₀ of the single-layered die-bonding thin film was as high as 83° C., and the embedding property of the die-bonding thin film in the substrate was poor. On the other hand, the post-dipping adhesion and non-dipping adhesion between the cured product of the die-bonding film and the mirror-surface silicon wafer were both 10 N/25 mm or more as in the cases of Examples 1 to 2.

[Industrial Availability] The present invention provides a die-bonding film capable of suppressing transfer defects to the semiconductor wafer at the time of pick-up of a semiconductor wafer of small size, and can be well embedded in a substrate during die-bonding, and a dicing die-bonding having the die-bonding film. A wafer and a method of manufacturing a semiconductor wafer using the dicing die-bonding wafer are extremely useful industrially.

1A, 1B, 1C, 1D‧‧‧Cutting die bonding pads 10‧‧‧Support sheet (cutting sheet) 12‧‧‧Interlayer 13, 23‧‧‧Die Bonding Film 131, 231‧‧‧1st floor 131’‧‧‧First layer after cutting 132, 232‧‧‧2nd floor 132’‧‧‧Second layer after cutting 1320’‧‧‧Second layer after cutting and hardened 9‧‧‧Semiconductor Wafers 9’‧‧‧Semiconductor Chip 101‧‧‧Laminated body (1-2) (Laminated body (1), Laminated body (1-1)) 102‧‧‧Laminates (2) 103‧‧‧Laminates(3)

[FIG. 1] A cross-sectional view schematically showing a die-bonding thin film according to an embodiment of the present invention. [FIG. 2] It is a cross-sectional view schematically showing a dicing die-bonding sheet according to an embodiment of the present invention. [FIG. 3] It is a cross-sectional view schematically showing a dicing die-bonding sheet according to an embodiment of the present invention. [FIG. 4] It is a cross-sectional view schematically showing a dicing die-bonding sheet according to an embodiment of the present invention. [FIG. 5] It is a cross-sectional view schematically showing a dicing die-bonding sheet according to an embodiment of the present invention. [FIG. 6] It is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. FIG. 7 is a cross-sectional view schematically showing an example of a state in which a semiconductor wafer with a cured die-bonding film obtained by the present invention is die-bonded to a circuit-forming surface of a substrate.

Claims (3)

A die-bonding film, comprising a first layer and a second layer on the first layer, wherein the first layer has a characteristic that the initial detection temperature of the melt viscosity is 75° C. or lower, the second layer has adhesiveness and Energy ray hardenability, and the die-bonding film has the following characteristics: the second layer with a thickness of 10 μm and a width of more than 25 mm is used as a test piece, and the test piece is attached to a silicon mirror wafer (silicon mirror wafer), and cut The test piece was cut to a width of 25 mm, the cut test piece and the mirror-surface silicon wafer were immersed in pure water for 2 hours, and then the test piece after immersion was irradiated with energy rays to harden it into a cured product. When producing the laminated body for testing in which the cured product is attached to the mirror-surface silicon wafer, the adhesive force between the cured product with a width of 25 mm and the mirror-surface silicon wafer is 6N/25mm or more. A dicing die-bonding sheet includes a support sheet and the die-bonding film as described in claim 1 on the support sheet, wherein the first layer in the die-bonding film is disposed on the support sheet side. A method of manufacturing a semiconductor wafer, comprising: forming a die-bonding film as described in claim 1, attaching a semiconductor wafer to the second layer, and attaching a dicing sheet to the first layer. body (1-1), or a laminated body (1- 2); via a dicing knife, the layered body (1-1) or the semiconductor wafer in the layered body (1-2) is cut together with the die-bonding film to produce the first layer having the cut-off , the second layer after cutting, and the layered body (2) of semiconductor wafers of the semiconductor wafer after cutting; by curing the second layer after cutting in the layered body (2) with energy rays, hardening is formed thing, making The layered body (3) of the first layer after cutting, the cured product, and the semiconductor wafer; in the layered body (3), the semiconductor wafer having the first layer after cutting and the cured product is obtained from The cutting piece or the support piece is separated and picked up.

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