TW202141603A - Sheet for production of semiconductor device and method for producing semiconductor chip with film-form adhesive - Google Patents

Abstract

A sheet (101) for the production of a semiconductor device, said sheet being provided with a base material (11), an adhesive layer (12), an intermediate layer (13) and a film-form adhesive (14). This sheet for the production of a semiconductor device has a configuration wherein the adhesive layer (12), the intermediate layer (13) and the film-form adhesive (14) are sequentially superposed on the base material (11) in this order; the film-form adhesive (14) contains an antistatic agent; the content ratio of the antistatic agent relative to the total mass of the film-form adhesive (14) is 3% by mass or less; the intermediate layer (13) contains, as a main component, a non-silicon resin that has a weight average molecular weight of 100,000 or less; and the intermediate layer (13)-side surface of the film-form adhesive (14) has a surface resistivity of 1 * 10<SP>13</SP> [Omega] or less.

Description

Sheet for manufacturing semiconductor device and method for manufacturing semiconductor wafer with film-like adhesive

The present invention relates to a manufacturing method of a sheet for manufacturing a semiconductor device and a semiconductor wafer with a film-like adhesive. This application is based on Japanese Patent Application No. 2020-058734 filed in Japan on March 27, 2020 and claims priority, and the content of the application is used here.

When manufacturing a semiconductor device, a semiconductor wafer with a film-like adhesive is used. The semiconductor wafer with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on the inner surface of the semiconductor wafer. As an example of the manufacturing method of the semiconductor wafer with a film-like adhesive agent, the method shown below can be mentioned, for example.

First, attach a dicing die-bonding sheet to the inner surface of the semiconductor wafer. Examples of the dicing bonding wafer include those provided with a support sheet and a film-like adhesive provided on the surface of the support sheet. The supporting sheet can be used as a cutting sheet. As the support sheet, there are, for example, a support sheet having a substrate and an adhesive layer provided on one surface of the substrate, and a support sheet having different configurations such as those composed of only the substrate. The outermost surface of the support sheet with the adhesive layer on the adhesive layer side becomes the surface where the film-like adhesive is provided. The dicing adhesive chip is attached to the inner surface of the semiconductor wafer by the film-like adhesive in the dicing adhesive chip.

Then, the semiconductor wafer on the support sheet and the film-like adhesive are cut together by dicing with a blade. The "cutting" of the semiconductor wafer is also called "segmentation", whereby the semiconductor wafer is singulated into the target semiconductor chip. The film adhesive is cut along the outer periphery of the semiconductor wafer. Thereby, a semiconductor chip with a film-like adhesive can be obtained, and a group of semiconductor chips with a film-like adhesive can be obtained. The semiconductor chip with the film-like adhesive is provided with a semiconductor chip and arranged on the inner surface of the semiconductor chip After cutting the film-like adhesive, the above-mentioned semiconductor wafer group with the film-like adhesive is arranged on the support sheet and holds a plurality of these semiconductor wafers with the film-like adhesive in a neatly arranged state.

Then, the semiconductor wafer with the film-like adhesive is pulled away from the supporting sheet and picked up. In the case of using a support sheet with a hardening adhesive layer, at this time, the adhesive layer is hardened to reduce the adhesiveness, and picking up becomes easier. Through the above operations, a semiconductor wafer with a film-like adhesive for manufacturing a semiconductor device is obtained.

As another example of the method of manufacturing a semiconductor wafer with a film-like adhesive, for example, the method shown below can be cited. First, a back polishing tape (sometimes called "surface protection tape") is attached to the circuit formation surface of the semiconductor wafer. Then, a predetermined segmentation part is set inside the semiconductor wafer, the area contained in the part is set as a focus, and the laser light is irradiated to focus on the focus, thereby forming a modified layer inside the semiconductor wafer. Then, a grinder is used to grind the inner surface of the semiconductor wafer, thereby adjusting the thickness of the semiconductor wafer to a target value. By using the grinding force applied to the semiconductor wafer at this time, the semiconductor wafer is divided (singulated) at the formation portion of the modified layer to produce a plurality of semiconductor wafers. The method of dividing the semiconductor wafer with the formation of the modified layer is called stealth dicing (registered trademark), and while irradiating the semiconductor wafer with laser light to cut off the irradiated part of the semiconductor wafer, Laser cutting in which semiconductor wafers are gradually cut from the surface is completely different in nature.

Furthermore, one sticky wafer is attached to the above-mentioned ground surface (in other words, the ground surface) of all the semiconductor wafers fixed on the back grinding tape. As the bonding wafer, the same as the above-mentioned dicing bonding wafer can be mentioned. The sticky wafer is not used in the dicing of semiconductor wafers like this, and it can sometimes be designed to have the same structure as the dicing sticky wafer. The adhesive chip is also attached to the inner surface of the semiconductor chip by the film-like adhesive in the adhesive chip.

Then, after removing the back polishing tape from the semiconductor chip, the bonded chip is cooled while stretching in a direction parallel to the surface of the bonded chip (for example, the attaching surface of the film-like adhesive to the semiconductor chip) The so-called expansion (cold expansion), whereby the film-like adhesive is cut along the outer periphery of the semiconductor wafer. Through the above operations, a semiconductor chip with a film-like adhesive is obtained. The semiconductor chip with a film-like adhesive is provided with a semiconductor chip and a cut-off film-like adhesive provided on the inner surface of the semiconductor chip.

Then, as in the case of cutting with a blade as described above, the semiconductor wafer with the film-like adhesive is pulled from the supporting sheet and picked up, thereby obtaining a semiconductor wafer with the film-like adhesive for manufacturing a semiconductor device.

Both dicing and bonding wafers can be used to manufacture semiconductor chips with film-like adhesives, and finally target semiconductor devices can be manufactured. In this specification, dicing and bonding chips are referred to as "sheets for manufacturing semiconductor devices".

As a sheet for manufacturing semiconductor devices, for example, a dicing die-bonding tape (equivalent to the aforementioned dicing die-attachment) is disclosed. The dicing die-bonding tape has a substrate layer (equivalent to the aforementioned support sheet) and an adhesive layer (equivalent to the aforementioned film-like Adhesive) Direct contact and laminated structure (refer to Patent Document 1). It is generally believed that the 90-degree peeling force of the substrate layer and the adhesive layer at -15°C is adjusted to a specific range in the dicing die-bonding tape, so that the adhesive layer can be separated with high precision by expansion. In addition, it is generally believed that since the 90 degree peeling force of the substrate layer and the adhesive layer at 23°C is adjusted to a specific range, when the dicing die-bonding tape is used, the semiconductor wafer with the adhesive layer can be picked up without difficulty (Equivalent to the aforementioned semiconductor wafer with a film-like adhesive), and can prevent the semiconductor wafer and the semiconductor wafer from peeling off the adhesive layer during the process until the pick-up.

On the other hand, the semiconductor chip after pickup is bonded to the circuit surface of the circuit board with a film-like adhesive, and after wire bonding, the whole is sealed with resin. Using the semiconductor package thus obtained, the target semiconductor device is finally manufactured.

In addition, Patent Document 2 discloses a film for a semiconductor device (corresponding to the aforementioned dicing die) in which an adhesive film with a dicing sheet is laminated on the coating film at a predetermined interval. It is stated here that in order to prevent the generation of static electricity or the resulting charging of semiconductor wafers and the like and circuit breakage, an antistatic agent or conductive substance can be added to the substrate, adhesive layer or adhesive film. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2018-56289. [Patent Document 2] JP 2012-59768 A.

[The problem to be solved by the invention]

However, although the dicing die-bonding tape disclosed in Patent Document 1 is suitable for stealth cutting (registered trademark), it is not suitable for blade cutting. If the dicing die-bonding tape is used for blade dicing, it is easy to produce whisker-like cutting chips from the substrate layer (sometimes called "Whisker" in this field), which is suitable for dividing semiconductor wafers. Degrade.

In addition, if an antistatic agent is used for the film-like adhesive in order to prevent the generation of static electricity, the reliability of the semiconductor package obtained by using the aforementioned film-like adhesive may be impaired.

The object of the present invention is to provide a sheet for manufacturing a semiconductor device and a method for manufacturing a semiconductor wafer with a film-like adhesive using the sheet for manufacturing a semiconductor device. The film adhesive contains an antistatic agent, and the semiconductor package obtained by using the film adhesive has excellent reliability. [Means to solve the problem]

The present invention has the following aspects. [1] A sheet for manufacturing semiconductor devices, comprising a substrate, an adhesive layer, an intermediate layer, and a film adhesive, and the adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated on the substrate The film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3% by mass or less; the intermediate layer contains a non-static agent with a weight average molecular weight of 100,000 or less Silicon resin is the main component; the surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less. [2] The semiconductor device manufacturing sheet according to [1], wherein when the surface of the intermediate layer on the film adhesive side is analyzed by X-ray photoelectron spectroscopy, the concentration of silicon is relative to carbon and oxygen The ratio of the total concentration of, nitrogen and silicon becomes 1% to 20%. [3] The sheet for manufacturing a semiconductor device as described in [1] or [2], wherein the intermediate layer contains an ethylene-vinyl acetate copolymer or polyolefin as the non-silicon-based resin. [4] The semiconductor device manufacturing sheet according to [3], wherein the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin; in the ethylene-vinyl acetate copolymer, it is derived from vinyl acetate The ratio of the mass of the structural unit derived from the ester to the total mass of all the structural units is 10% by mass to 40% by mass. [5] The semiconductor device manufacturing sheet according to [4], wherein the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin and a silicone-based compound; in the intermediate layer, the The ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer is 90% to 99.99% by mass; in the intermediate layer, the content of the silicone compound is relative to the total mass of the intermediate layer The ratio of is 0.01% by mass to 10% by mass. [6] A method of manufacturing a semiconductor wafer with a film-like adhesive, comprising the steps of: applying the above-mentioned film-like adhesive of the semiconductor device manufacturing sheet as described in any one of [1] to [5] The step of attaching the inner surface of the semiconductor wafer to the exposed surface to obtain a laminate composed of the substrate, the adhesive layer, the intermediate layer, the film adhesive, and the semiconductor wafer in sequence; The step of dividing the wafer and cutting the film-like adhesive to obtain a semiconductor chip with the film-like adhesive; and pulling away the semiconductor with the film-like adhesive from the substrate, the adhesive layer and the intermediate layer The step of picking up the wafer. [7] A method of manufacturing a semiconductor wafer with a film-like adhesive, comprising the steps of: applying the above-mentioned film-like adhesive of the semiconductor device manufacturing sheet as described in any one of [1] to [5] The exposed surface is attached to the inner surface of the semiconductor chip group in which a plurality of the semiconductor chips are neatly arranged, and the substrate, the adhesive layer, the intermediate layer, the film adhesive, and the semiconductor chip group are sequentially obtained The step of laminating the laminate formed by the layer; the step of cutting the film-like adhesive to obtain a semiconductor chip with the film-like adhesive; and separating the film from the substrate, the adhesive layer and the intermediate layer The step of picking up semiconductor wafers with adhesives. [Efficacy of invention]

According to the present invention, it is possible to provide a sheet for manufacturing a semiconductor device and a method for manufacturing a semiconductor wafer with a film-like adhesive using the sheet for manufacturing a semiconductor device, wherein the sheet-based semiconductor wafer for manufacturing a semiconductor device has excellent division suitability, and The film-like adhesive contains an antistatic agent, and the reliability of the package is excellent.

◇Semiconductor device manufacturing sheet The semiconductor device manufacturing sheet of one embodiment of the present invention includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and the adhesive layer is sequentially laminated on the substrate, The intermediate layer and the film-like adhesive are formed, the film-like adhesive contains an antistatic agent, the content of the antistatic agent relative to the total mass of the film-like adhesive is 3% by mass or less, and the intermediate layer contains A non-silicon resin having a weight average molecular weight of 100,000 or less is used as the main component, and the surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less.

When the semiconductor device manufacturing sheet of this embodiment is used as a dicing sticky wafer for blade dicing, since the semiconductor device manufacturing sheet is provided with the intermediate layer, it is possible to easily prevent the blade from reaching the substrate or the adhesive layer, thereby preventing Whisker-like cutting chips are generated from the base material or the adhesive layer (alias: Whisker, below are not limited to those derived from the base material or the adhesive layer, sometimes referred to as "cutting chips"). In addition, the use of a non-silicone resin with a weight average molecular weight of 100,000 or less, especially a weight average molecular weight of 100,000 or less, as the main component of the intermediate layer cut by a blade can also suppress the generation of cutting chips from the intermediate layer.

On the other hand, when the semiconductor device manufacturing sheet of this embodiment is used as a bonding wafer to perform dicing (stealth dicing (registered trademark)) accompanying the formation of the modified layer in the semiconductor wafer, the aforementioned semiconductor device manufacturing sheet With the aforementioned intermediate layer, the semiconductor device manufacturing sheet is subsequently stretched in a direction parallel to the surface of the semiconductor device manufacturing sheet (for example, the attaching surface of the film-like adhesive to the semiconductor wafer) ( The so-called expansion), the film-like adhesive can be cut with high precision at the target site, and the cutting failure can be suppressed. It is considered that the reason is that by providing the intermediate layer, the expanded stress can be efficiently used for the distance expansion between the wafers.

In this way, the semiconductor device manufacturing sheet of the present embodiment can suppress the generation of cutting chips from the base material and the intermediate layer during the blade dicing, and can suppress the cutting failure of the film-like adhesive during the aforementioned expansion, and is useful when the semiconductor wafer is divided It has the characteristics of restraining the occurrence of defects, and the division suitability of semiconductor wafers is excellent.

In the semiconductor device manufacturing sheet of this embodiment, the film adhesive contains an antistatic agent, and the surface resistivity of the surface of the intermediate layer side of the film adhesive may be 1×10 ¹³ Ω or less, and It can prevent the generation of static electricity or the resulting charging of semiconductor wafers and the destruction of the circuit. In addition, in the semiconductor device manufacturing sheet of this embodiment, since the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3% by mass or less, the semiconductor package obtained by using the film adhesive is reliable Excellent performance, especially the reliability of a semiconductor package in the form of a chip/chip in which a semiconductor chip is laminated on a semiconductor chip.

The surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less, preferably 5×10 ¹¹ Ω or more and 1×10 ¹³ Ω or less, more preferably 1×10 ¹² Ω or more To 8×10 ¹² Ω or less.

Examples of the antistatic agent contained in the film-like adhesive include carbon materials, ionic materials, metal fine particles, metal oxides, metal fillers, and surfactants. From the viewpoint of further exhibiting the effect of the present embodiment, the antistatic agent preferably includes at least one selected from the group consisting of carbon materials and ionic materials. Examples of carbon materials include carbon nanotubes, carbon nanofibers, graphene, carbon black, ground carbon fibers, graphite, and the like. Commercial products can also be used for these materials. These carbon materials can be used individually by 1 type or in combination of 2 or more types. The carbon material is preferably at least one selected from the group consisting of carbon nanotubes, graphene, and carbon black. The ionic material is preferably at least one selected from the group consisting of ionic liquids and ionic polymers.

The ratio of the content of the antistatic agent to the total mass of the film-like adhesive is 3% by mass or less, and may be 0.1% by mass or more and 3.0% by mass or less, or 0.2% by mass or more and 3.0% by mass or less, It may be 0.3% by mass or more and 3.0% by mass or less, 0.4% by mass or more and 3.0% by mass or less, or 0.5% by mass or more and 2.9% by mass or less.

In this specification, the "weight average molecular weight", unless otherwise specified, is a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method.

The method of using the semiconductor device manufacturing sheet of this embodiment will be described in detail below.

Hereinafter, the sheet for manufacturing a semiconductor device of this embodiment will be described in detail with reference to the drawings. In addition, the drawings used in the following description may sometimes be enlarged to show the main parts for easy understanding of the characteristics of the present invention, and the dimensional ratios of the constituent elements may not necessarily be the same as the actual ones.

FIG. 1 is a cross-sectional view schematically showing a sheet for manufacturing a semiconductor device according to an embodiment of the present invention, and FIG. 2 is a plan view of the sheet for manufacturing a semiconductor device shown in FIG. 1. In addition, in the figures following FIG. 2, the same components as those shown in the already-explained figures are denoted by the same reference numerals as in the already-explained figures, and detailed explanations are omitted.

The sheet 101 for manufacturing a semiconductor device shown here is provided with a base material 11, and an adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 are laminated on the base material 11 in this order. The sheet 101 for manufacturing a semiconductor device further includes a release film 15 on a surface (hereinafter sometimes referred to as a "first surface") 14a on the opposite side of the film-like adhesive 14 to the side where the intermediate layer 13 is provided.

In the sheet 101 for manufacturing a semiconductor device, an adhesive layer 12 is provided on one side of the substrate 11 (in this specification, sometimes referred to as the "first side") 11a. An intermediate layer 13 is provided on the surface 12a of the adhesive layer 12 opposite to the side on which the base material 11 is provided (in this specification, it may be referred to as the "first surface"). A film-like adhesive 14 is provided on the surface 13a of the intermediate layer 13 opposite to the side on which the adhesive layer 12 is provided (in this specification, it may be referred to as the "first surface"). A release film 15 is provided on the first surface 14a of the film-like adhesive 14. In this way, the sheet 101 for manufacturing a semiconductor device is constructed by laminating the base material 11, the adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 in this order in the thickness direction of these layers.

The sheet 101 for manufacturing a semiconductor device is in a state where the release film 15 is removed, and the first surface 14a of the film-like adhesive 14 in the sheet 101 for manufacturing a semiconductor device is attached to a semiconductor wafer, a semiconductor wafer, or an incomplete pass. Divide the inner surface of a semiconductor wafer (not shown) for use.

In this specification, in the case of a semiconductor wafer and a semiconductor wafer, the surface on which the circuit is formed is called the "circuit formation surface", and the surface on the opposite side to the circuit formation surface is called the "inner surface" ".

In this specification, a laminate having a structure in which a substrate and an adhesive layer are laminated in the thickness direction without an intermediate layer is sometimes referred to as a "support sheet". In Fig. 1, reference symbol 1 represents a support sheet. In addition, a laminate having a structure in which a substrate, an adhesive layer, and an intermediate layer are laminated in the thickness direction in this order is sometimes referred to as a "laminated sheet." In FIG. 1, the reference symbol 10 represents a laminated sheet. The laminate of the support sheet and the intermediate layer is included in the laminate sheet.

The intermediate layer 13 and the film adhesive 14 of the label portion 30 are both circular in plan when viewed from above these layers. The diameter of the intermediate layer 13 is the same as the diameter of the film adhesive 14. Furthermore, in the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 are arranged so that the centers are aligned. In other words, the outer peripheral positions of the intermediate layer 13 and the film-like adhesive 14 are uniform in the radial direction. Configure in a consistent way.

The area of the first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 are both smaller than the area of the first surface 12a of the adhesive layer 12. Moreover, the maximum value (ie diameter) of the width W ₁₃ of the intermediate layer 13 and the maximum value (ie the diameter) of the width W ₁₄ of the film adhesive 14 are both smaller than the maximum value of the width W 13 of the adhesive layer 12 and the base material 11 The maximum value of the width. Therefore, in the sheet 101 for manufacturing a semiconductor device, a part of the first surface 12 a of the adhesive layer 12 is not covered by the intermediate layer 13 and the film-like adhesive 14. The area where the intermediate layer 13 and the film-like adhesive 14 are not laminated on the first surface 12a of the adhesive layer 12 is in direct contact with the release film 15 being laminated, and the area is exposed when the release film 15 is removed (Hereinafter, this area may be referred to as "non-layered area" in this specification). Furthermore, in the semiconductor device manufacturing sheet 101 provided with the release film 15, in the area of the adhesive layer 12 not covered by the intermediate layer 13 and the film-like adhesive 14, there may be an unlaminated release film 15 as shown here The area may not exist.

The sheet 101 for manufacturing a semiconductor device in a state where the film-like adhesive 14 is not cut and is attached to the above-mentioned semiconductor wafer or semiconductor wafer, etc. by the film-like adhesive 14 can be fixed by the following method: A part of the aforementioned non-laminated area in the adhesive layer 12 of the manufacturing sheet 101 is attached to a jig such as a ring frame for fixing a semiconductor wafer. Therefore, it is not necessary to separately provide a jig adhesive layer for fixing the semiconductor device manufacturing sheet 101 to the aforementioned jig in the semiconductor device manufacturing sheet 101. Furthermore, since there is no need to provide an adhesive layer for a jig, the sheet 101 for manufacturing a semiconductor device can be manufactured inexpensively and efficiently.

In this way, the sheet 101 for manufacturing a semiconductor device exhibits an advantageous effect by not having an adhesive layer for a jig, but it may also be provided with an adhesive layer for a jig. In this case, the adhesive layer for a jig is provided in the area near the peripheral edge part of the surface of any one layer which comprises the sheet|seat 101 for semiconductor device manufacture. Examples of such a region include the aforementioned non-laminated region in the first surface 12a of the adhesive layer 12, and the like.

The adhesive layer for a jig may be a well-known one, for example, it may have a single-layer structure containing an adhesive component, or a multilayer structure in which a layer containing an adhesive component is layered on both areas of a sheet that becomes a core material.

In addition, the sheet 101 for manufacturing a conductor device is stretched in a direction parallel to the surface of the sheet 101 for manufacturing a semiconductor device (for example, the first surface 12a of the adhesive layer 12) as described later (so-called expansion) At this time, by the presence of the aforementioned non-layered region on the first surface 12a of the adhesive layer 12, the sheet 101 for manufacturing a semiconductor device can be easily expanded. Moreover, not only can the film-like adhesive 14 be easily cut, but the peeling of the intermediate layer 13 and the film-like adhesive 14 from the adhesive layer 12 may be suppressed.

In the sheet 101 for manufacturing a semiconductor device, the intermediate layer 13 contains a non-silicon resin having a weight average molecular weight of 100,000 or less as a main component.

The semiconductor device manufacturing sheet of this embodiment is not limited to those shown in FIGS. 1 and 2, and may be modified, deleted, or added to a part of the structure shown in FIGS. 1 and 2 within the scope that does not impair the efficacy of the present invention. .

For example, the sheet for manufacturing a semiconductor device of this embodiment may include other layers that do not correspond to any of the base material, the adhesive layer, the intermediate layer, the film-like adhesive, the release film, and the adhesive layer for jigs. However, the semiconductor device manufacturing sheet of this embodiment is preferably as shown in FIG. The state is equipped with a film-like adhesive.

For example, in the semiconductor device manufacturing sheet of this embodiment, the planar shape of the intermediate layer and the film-like adhesive may be a shape other than a circular shape, and the planar shapes of the intermediate layer and the film-like adhesive may be the same or different from each other. In addition, the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are preferably smaller than those of the surface of the layer closer to the substrate side (for example, the first surface of the adhesive layer). , Can be the same as each other or different. Moreover, the positions of the intermediate layer and the outer periphery of the film-like adhesive may be the same in the radial direction, or they may not be consistent. Next, each layer constituting the semiconductor device manufacturing sheet of this embodiment will be described in detail.

○Substrate The aforementioned substrate is in the form of a sheet or film. The constituent material of the aforementioned base material is preferably various resins. Specifically, for example, polyethylene (low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), etc.) can be cited. ), polypropylene (PP), polybutene, polybutadiene, polymethylpentene, styrene-ethylene butene-styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyterephthalene Ethylene formate (PET), polybutylene terephthalate (PBT), polyurethane, polyacrylate urethane, polyimide (PI), ionomer resin, ethylene- (Meth) acrylic copolymer, ethylene-(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer and ethylene-(meth)acrylate copolymer other than ethylene copolymer, polystyrene, poly Carbonate, fluororesin, hydrogenated product, modified product, crosslinked product or copolymer of any of these resins, etc.

Furthermore, in this specification, the so-called "(meth)acrylic acid" refers to the concept including both "acrylic acid" and "methacrylic acid". Terms similar to (meth)acrylic acid are also the same. For example, the so-called "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate". The so-called "(meth)acrylic acid ester" ", is a concept that includes both "acrylic acid group" and "methacrylic acid group".

The resin constituting the substrate may be only one type or two or more types. In the case of two or more types, the combination and ratio of these resins can be arbitrarily selected.

The substrate may be composed of only one layer (single layer), or may be composed of multiple layers of two or more layers. When the substrate is composed of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired. In this specification, it is not limited to the case of the base material. The so-called "multilayers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only a part of the layers may be different", Furthermore, "the layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

The thickness of the substrate can be appropriately selected according to the purpose, and is preferably 50 μm to 300 μm, more preferably 60 μm to 150 μm. By making the thickness of the substrate more than the aforementioned lower limit, the structure of the substrate becomes more stable. Since the thickness of the base material is below the aforementioned upper limit, the film-like adhesive can be cut more easily during blade dicing and during the aforementioned expansion of the semiconductor device manufacturing sheet. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of the substrate composed of multiple layers means the total thickness of all layers constituting the substrate. In this manual, "thickness" can be expressed as a value expressed by measuring the thickness at 5 randomly selected locations and averaging, unless otherwise specified, according to JIS (Japanese Industrial Standards) K7130, using a constant pressure Obtained by a thickness measuring device.

The substrate may also be subjected to the following treatments on the surface in order to improve the adhesion with other layers such as the adhesive layer provided on the substrate: unevenness by spray treatment, solvent treatment, embossing treatment, etc. Chemical treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. The surface of the substrate can also be primed. -The substrate may also have the following layers: antistatic coating; when the bonded wafer is stacked and stored, it prevents the substrate from adhering to other sheets or prevents the substrate from adhering to the layer of the suction table.

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

The optical properties of the substrate are not particularly limited within the range that does not impair the efficacy of the present invention. For example, the substrate can also penetrate laser light or energy rays.

The substrate can be manufactured by a known method. For example, a substrate containing resin (using resin as a constituent material) can be manufactured by molding the aforementioned resin or a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive. The adhesive layer can be formed using an adhesive composition containing the aforementioned adhesive. For example, the adhesive composition is applied to the surface to be formed of the adhesive layer, and dried as necessary, thereby forming the adhesive layer on the target site.

In the adhesive layer, the ratio of the total content of one or two or more of the following contained components of the adhesive layer to the total mass of the adhesive layer does not exceed 100% by mass. Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following contained components of the adhesive composition to the total mass of the adhesive composition does not exceed 100% by mass.

The application of the adhesive composition may be performed by a known method, for example, the use of an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, Curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater and other coating machine methods.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferably heated and dried. In this case, for example, it is preferably at 70°C to 130°C for 10 seconds. Dry conditions to 5 minutes.

Examples of the aforementioned adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. It is preferably an acrylic resin.

Furthermore, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resins include not only those with adhesiveness of the resin itself, but also resins that exhibit adhesiveness by being used in combination with other ingredients such as additives, or those that exhibit adhesiveness by the presence of heat or water triggering. Resin etc.

The adhesive layer may be either curable or non-curable, for example, it may be either energy-ray curable or non-energy-ray curable. The hardening adhesive layer can easily adjust the physical properties before and after hardening.

In this specification, the so-called "energy line" refers to an electromagnetic wave or charged particle beam with energy quantum. Examples of energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode) lamp as the ultraviolet source, for example. The electron beam can be irradiated by an electron beam accelerator or the like. In addition, in this specification, the "energy ray curability" means the property of being hardened by irradiation with energy rays, and the "non-energy ray hardening property" means the property of not being hardened even if it is irradiated with energy rays.

The adhesive layer may be composed of only one layer (single layer), or may be composed of multiple layers of two or more layers. In the case of being composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the first adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

The optical properties of the adhesive layer are not particularly limited within a range that does not impair the efficacy of the present invention. For example, the adhesive layer can also allow energy rays to penetrate. Next, the aforementioned adhesive composition will be described. The following adhesive composition can contain one or more of the following components so that the total content (mass%) does not exceed 100% by mass, for example.

[Adhesive composition] When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive composition, for example, the following adhesive composition can be cited: The adhesive composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)") and an energy-ray curable compound; Adhesive composition (I-2), contained in the side chain of non-energy-ray-curable adhesive resin (I-1a), energy-ray-curable adhesive resin (I-2a) with unsaturated groups introduced into the side chain (below Sometimes referred to simply as "adhesive resin (I-2a)"); and the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

[Adhesive composition (I-1)] The aforementioned adhesive composition (I-1) contains a non-energy-ray-curable adhesive resin (I-1a) and an energy-ray-curable compound as described above.

[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. As said acrylic resin, the acrylic polymer which has at least the structural unit derived from alkyl (meth)acrylate is mentioned, for example. The aforementioned acrylic resin may have only one type of structural unit, or two or more types. In the case of two or more types, the combination and ratio of these structural units can be arbitrarily selected.

The adhesive composition (I-1) contains only one type of adhesive resin (I-1a), or two or more types. In the case of two or more types, these adhesive resins (I-1a) The combination and ratio can be chosen arbitrarily.

In the adhesive composition (I-1), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-1) is preferably 5 to 99% by mass, and more It is preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.

[Energy ray hardening compound] Examples of the energy ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by energy ray irradiation. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (Meth)acrylate such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylate aminomethyl Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above. The energy ray curable compound is preferably (meth)acrylate urethane and (meth)acrylate urethane in terms of relatively large molecular weight and difficult to reduce the storage elastic modulus of the adhesive layer. Ester oligomers.

The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds may be Free to choose.

In the adhesive composition (I-1), the ratio of the content of the aforementioned energy ray curable compound to the total mass of the adhesive composition (I-1) is preferably 1% to 95% by mass, more preferably 5 mass% to 90 mass%, particularly preferably 10 mass% to 85% by mass.

[Crosslinking agent] When using the aforementioned acrylic polymer having structural units derived from functional group-containing monomers in addition to the structural units derived from alkyl (meth)acrylates as the adhesive resin (I-1a), the adhesive The composition (I-1) preferably further contains a crosslinking agent.

The aforementioned crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resins (I-1a). Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of these diisocyanates; ethylene diisocyanate Epoxy crosslinking agent such as alcohol glycidyl ether (crosslinking agent with glycidyl group); aziridine crosslinking agent such as hexa[1-(2-methyl)-aziridinyl] triphosphatriazine Agent (crosslinking agent with aziridinyl group); metal chelate crosslinking agent (crosslinking agent with metal chelate structure) such as aluminum chelate; isocyanurate crosslinking agent (with Crosslinking agent of isocyanuric acid skeleton) and so on. The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of enhancing the cohesive force of the adhesive and enhancing the adhesive force of the adhesive layer, as well as easy availability.

The adhesive composition (I-1) may contain only one type of crosslinking agent, or two or more types. In the case of two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

In the case of using a crosslinking agent, in the aforementioned adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 parts by mass to 100 parts by mass relative to the content of the adhesive resin (I-1a) 50 parts by mass, more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator fully undergoes a curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Thioether compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetin; benzil; benzil; benzophenone; 2,4-diethylthioxanthone ; 1,2-Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and the like. In addition, as the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators can be arbitrary choose.

In the case of using a photopolymerization initiator, in the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 parts by mass relative to the content of the aforementioned energy ray curable compound 100 parts by mass It is 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives] The adhesive composition (I-1) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. As the aforementioned other additives, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Known additives such as reaction delay agents and crosslinking accelerators (catalysts).

Furthermore, the so-called reaction delay agent is, for example, used to inhibit the effect of the catalyst mixed in the adhesive composition (I-1) from performing unintended effects in the adhesive composition (I-1) during storage. Component of sexual cross-linking reaction. Examples of the reaction delay agent include those that form chelate complexes by chelation to a catalyst, and more specifically include those having two or more carbonyl groups (-C(=O)-) in one molecule.

The other additives contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these other additives may be arbitrarily selected.

The content of the other additives of the adhesive composition (I-1) is not particularly limited, as long as it is appropriately selected according to the type.

[Solvent] The adhesive composition (I-1) may also contain a solvent. By containing a solvent, the adhesive composition (I-1) has improved applicability to the surface to be coated.

The aforementioned solvent is preferably an organic solvent.

[Adhesive composition (I-2)] As described above, the aforementioned adhesive composition (I-2) is contained in the side chain of the non-energy-ray-curable adhesive resin (I-1a) and the energy-ray-curable adhesive resin (I-1a) with unsaturated groups introduced into the side chain -2a).

[Adhesive resin (I-2a)] The aforementioned adhesive resin (I-2a) is obtained, for example, by reacting an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group with a functional group in the adhesive resin (I-1a).

The aforementioned unsaturated group-containing compound has the aforementioned energy ray polymerizable unsaturated group, and further has the ability to bond with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) The base compound. Examples of the energy-beam polymerizable unsaturated group include (meth)acrylic acid group, vinyl group (ethenyl), allyl group (2-propenyl group), and the like, and (meth)acrylic acid group is preferred. Examples of groups capable of bonding to functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding to hydroxyl groups or amino groups, and groups capable of bonding to carboxyl groups or epoxy groups. The hydroxyl and amino groups, etc.

Examples of the aforementioned unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, and the like.

The adhesive composition (I-2) contains only one type of adhesive resin (I-2a), or two or more types. In the case of two or more types, these adhesive resins (I-2a) The combination and ratio can be chosen arbitrarily.

In the adhesive composition (I-2), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) is preferably 5 to 99% by mass, and more It is preferably 10% by mass to 95% by mass, and particularly preferably 10% by mass to 90% by mass.

[Crosslinking agent] For example, when the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the adhesive composition ( I-2) may further contain a crosslinking agent.

As the aforementioned crosslinking agent in the adhesive composition (I-2), the same ones as the crosslinking agent in the adhesive composition (I-1) can be cited. The adhesive composition (I-2) may contain only one type of crosslinking agent, or two or more types. In the case of two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

In the case of using a cross-linking agent, in the aforementioned adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 parts by mass to 100 parts by mass of the adhesive resin (I-2a). 50 parts by mass, more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing the photopolymerization initiator fully undergoes the curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the aforementioned photopolymerization initiator in the adhesive composition (I-2) include the same ones as the photopolymerization initiator in the adhesive composition (I-1). The adhesive composition (I-2) may contain only one type of photopolymerization initiator, or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators can be arbitrary choose.

In the case of using a photopolymerization initiator, in the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 relative to 100 parts by mass of the adhesive resin (I-2a) Parts by mass to 20 parts by mass, more preferably from 0.03 parts by mass to 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-2) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-2), the same ones as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents can be arbitrarily selected . The content of the other additives and the solvent of the adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the type.

[Adhesive composition (I-3)] As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray curable compound.

In the adhesive composition (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-3) is preferably 5 to 99% by mass, and more It is preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.

[Energy ray hardening compound] Examples of the aforementioned energy ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have energy ray polymerizable unsaturated groups and can be cured by energy ray irradiation, including It is the same as the energy ray curable compound contained in the adhesive composition (I-1). The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds may be Free to choose.

In the aforementioned adhesive composition (I-3), relative to 100 parts by mass of the adhesive resin (I-2a), the content of the aforementioned energy ray curable compound is preferably 0.01 to 300 parts by mass, more preferably It is 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator fully undergoes a curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the aforementioned photopolymerization initiator in the adhesive composition (I-3) include the same ones as the photopolymerization initiator in the adhesive composition (I-1). The adhesive composition (I-3) may contain only one type of photopolymerization initiator, or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators can be arbitrary choose.

In the case of using a photopolymerization initiator, in the adhesive composition (I-3), with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound, photopolymerization The content of the starting agent is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, and particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-3) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-3), the same ones as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents can be arbitrarily selected . The content of the other additives and the solvent of the adhesive composition (I-3) is not particularly limited, and may be appropriately selected according to the type.

[Adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)] So far, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been mainly described, but the description can also be made as the components contained in these The same applies to all adhesive compositions other than these three adhesive compositions (in this specification, referred to as "adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)) ").

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy-ray-curable adhesive composition, non-energy-ray-curable adhesives can also be cited Composition. Examples of non-energy-ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and esters. The adhesive composition (I-4) of a non-energy-ray-curable adhesive resin (I-1a) such as resin preferably contains an acrylic resin.

Adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or two or more crosslinking agents, and the content of the crosslinking agent can be set to be the same as the above The adhesive composition (I-1) is the same.

[Adhesive composition (I-4)] Preferred examples of the adhesive composition (I-4) include an adhesive composition containing the aforementioned adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include those that are the same as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive composition (I-4) contains only one type of adhesive resin (I-1a), or two or more types. In the case of two or more types, these adhesive resins (I-1a) The combination and ratio can be chosen arbitrarily.

In the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-4) is preferably 5 to 99% by mass, and more It is preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.

[Crosslinking agent] When using the aforementioned acrylic polymer having structural units derived from functional group-containing monomers in addition to the structural units derived from alkyl (meth)acrylate as the adhesive resin (I-1a), adhesion The agent composition (I-4) preferably further contains a crosslinking agent.

As the crosslinking agent in the adhesive composition (I-4), the same ones as the crosslinking agent in the adhesive composition (I-1) can be cited. The adhesive composition (I-4) may contain only one type of crosslinking agent, or two or more types. In the case of two or more types, the combination and ratio of these crosslinking agents can be arbitrarily selected.

In the aforementioned adhesive composition (I-4), relative to 100 parts by mass of the adhesive resin (I-1a), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 parts by mass Parts to 25 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass.

[Other additives, solvents] The adhesive composition (I-4) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention. In addition, the adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-4), the same ones as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents can be arbitrarily selected . The content of the other additives and the solvent of the adhesive composition (I-4) is not particularly limited, and can be appropriately selected according to the type.

[Manufacturing method of adhesive composition] Adhesive composition (I-1) to adhesive composition (I-3) or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition is obtained by blending the aforementioned adhesive and components other than the aforementioned adhesive if necessary to form the adhesive composition. The order of addition of each component is not particularly limited, and two or more components can also be added at the same time. In the case of using a solvent, it can be used by pre-diluting the compounding component by mixing the solvent with any compounding component other than the solvent. It is also possible not to pre-dilute any compounding component other than the solvent, but by combining the solvent with these The ingredients are mixed and used. The method of mixing each component at the time of compounding is not particularly limited, as long as it is appropriately selected from known methods such as the following methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; application The method of ultrasonic mixing. The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

○Composition for forming intermediate layer and intermediate layer The intermediate layer is in the form of a sheet or film, and contains the non-silicon resin as a main component. The intermediate layer may contain only non-silicon-based resin (constituted only by non-silicon-based resin), or may contain non-silicon-based resin and components other than the non-silicon-based resin.

The intermediate layer can be formed using, for example, a composition for forming an intermediate layer containing the aforementioned non-silicon resin. For example, the intermediate layer can be formed on the target site by applying the aforementioned composition for forming the intermediate layer on the surface to be formed of the intermediate layer, and drying if necessary.

In the intermediate layer, the ratio of the total content of one or two or more components of the intermediate layer to the total mass of the intermediate layer does not exceed 100% by mass. Similarly, in the composition for forming the intermediate layer, the ratio of the total content of one or two or more of the composition for forming the intermediate layer to the total mass of the composition for forming the intermediate layer to the total mass of the composition for forming the intermediate layer shall not exceed 100% by mass .

The application of the composition for forming the intermediate layer can be performed by the same method as the application of the above-mentioned adhesive composition.

The drying conditions of the composition for forming an intermediate layer are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferably heat-dried. In this case, for example, it is preferably dried at 60°C to 130°C for 1 minute to 6 minutes.

The weight average molecular weight of the aforementioned non-silicone resin is 100,000 or less. In terms of the further improvement of the splitting suitability of the semiconductor wafer of the semiconductor device manufacturing sheet, the weight average molecular weight of the non-silicon resin may be any of 80,000 or less, 60,000 or less, and 40,000 or less, for example.

The lower limit of the weight average molecular weight of the aforementioned non-silicone resin is not particularly limited. For example, the aforementioned non-silicone resin with a weight average molecular weight of 5000 or more is easier to obtain.

The weight average molecular weight of the aforementioned non-silicone resin can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit and any upper limit. For example, in one embodiment, the aforementioned weight average molecular weight may be any of 5000 to 100,000, 5,000 to 80,000, 5,000 to 60,000, and 5,000 to 40,000, for example.

In this embodiment, "the intermediate layer contains a non-silicone resin with a weight average molecular weight of 100,000 or less as the main component" means that "the intermediate layer can be fully utilized by containing a non-silicon resin with a weight average molecular weight of 100,000 or less. The amount of the obtained effect is to contain the aforementioned non-silicone resin". From this point of view, in the intermediate layer, the ratio of the content of the aforementioned non-silicone resin to the total mass of the intermediate layer (in other words, in the composition for forming the intermediate layer, the content of the aforementioned non-silicone resin relative to the solvent other than The ratio of the total content of all components) may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, for example, 95% by mass or more, 97% by mass or more, and 99% by mass Any of the above. On the other hand, the aforementioned ratio is 100% by mass or less.

The aforementioned non-silicon resin having a weight average molecular weight of 100,000 or less is not particularly limited as long as it is a resin component having a weight average molecular weight of 100,000 or less that does not have silicon atoms as constituent atoms. The aforementioned non-silicon resin may be, for example, any of a polar resin having a polar group and a non-polar resin having no polar group. For example, the non-silicon resin is preferably a polar resin in terms of high solubility in the intermediate layer forming composition and higher coating suitability of the intermediate layer forming composition.

In this specification, unless otherwise specified, the so-called "non-silicone resin" means the non-silicone resin having the above-mentioned weight average molecular weight of 100,000 or less.

The aforementioned non-silicon resin may be, for example, a homopolymer of one type of monomer (in other words, having only one type of constituent unit), or a polymer of two or more types of monomers (in other words, having two or more types of monomers). Constituent unit) copolymer.

As said polar group, a carbonyloxy group (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), etc. are mentioned, for example.

The aforementioned polar resin may contain only a structural unit having a polar group, or may contain both a structural unit having a polar group and a structural unit not having a polar group.

As a structural unit which has the said polar group, the structural unit derived from vinyl acetate etc. are mentioned, for example. As a structural unit which does not have the said polar group, the structural unit derived from ethylene, etc. are mentioned, for example. The so-called "derivatization" mentioned here means the structural changes required for polymerization of the aforementioned monomers.

In the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is preferably from 5 to 70% by mass, for example, from 7.5% to 55% by mass and from 10% by mass to 10% by mass. Any one of 40% by mass. In other words, in the aforementioned polar resin, the ratio of the mass of the constituent units without polar groups to the total mass of all constituent units is preferably 30% to 95% by mass, for example, it can be 45% to 92.5% by mass and 60% by mass. Any one of mass% to 90 mass %. When the ratio of the mass of the constituent unit having the polar group is more than the aforementioned lower limit, the aforementioned polar resin will more significantly have the characteristic of containing the polar group. When the ratio of the mass of the constituent unit having the polar group is below the aforementioned upper limit, the aforementioned polar resin has the characteristic of not containing the polar group more moderately.

As said polar resin, ethylene-vinyl acetate copolymer etc. are mentioned, for example. Among them, as a preferred polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of constituent units derived from vinyl acetate to the total mass of all constituent units (in this specification, sometimes referred to as "The content of the constituent unit derived from vinyl acetate") may be 40% by mass or less, or 30% by mass or less, or 10% to 40% by mass, or 10% to 30% by mass . In other words, as a preferred polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of the structural unit derived from ethylene to the total mass of all the structural units may be 60% by mass or more, or 70 The mass% or more may be 60 mass% to 90 mass %, or 70 mass% to 90 mass %.

The non-polar resin is preferably a polyolefin, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), metallocene catalyst linear low-density polyethylene (metallocene LLDPE) ), medium density polyethylene (MDPE), high density polyethylene (HDPE) and other polyethylene (PE); polypropylene (PP), etc.

The composition for forming the intermediate layer and the aforementioned non-silicon resin contained in the intermediate layer may be only one type or two or more types. In the case of two or more types, the combination and ratio of these non-silicon type resins can be arbitrarily selected . The composition for forming an intermediate layer and the aforementioned non-silicon resin contained in the intermediate layer are preferably ethylene-vinyl acetate copolymer or polyolefin. For example, the composition for forming the intermediate layer and the intermediate layer may contain one or two or more non-silicon resins as polar resins, and no non-silicon resins as non-polar resins, and may also contain one or two or more as polar resins. The non-polar resin is a non-silicon-based resin and contains a non-silicon-based resin as a polar resin. It can also contain one or more of the non-silicon-based resin as a polar resin and a non-silicon-based resin as a non-polar resin. The composition for forming an intermediate layer and the intermediate layer preferably contain at least a non-silicon resin as a polar resin.

In the composition for forming the intermediate layer and the intermediate layer, the ratio of the content of the aforementioned non-silicone resin as a polar resin to the total content of the aforementioned non-silicone resin may be 50% by mass or more, preferably 80% by mass or more , More preferably 90% by mass or more, for example, it may be any of 95% by mass or more, 97% by mass or more, and 99% by mass or more. When the aforementioned ratio is equal to or higher than the aforementioned lower limit, the effect obtained by using the aforementioned polar resin can be more remarkably obtained. On the other hand, the aforementioned ratio is 100% by mass or less.

That is, in the composition for forming the intermediate layer and the intermediate layer, the ratio of the content of the non-silicon-based resin as the non-polar resin to the total content of the non-silicon-based resin is preferably 20% by mass or less, more preferably 10% by mass or less, for example, may be any of 5% by mass or less, 3% by mass or less, and 1% by mass or less. On the other hand, the aforementioned ratio is 0% by mass or more.

The composition for forming an intermediate layer preferably contains a solvent in addition to the aforementioned non-silicone resin in terms of good workability, and may also contain a component not equivalent to any of the aforementioned non-silicone resin and solvent (this In the specification, it is sometimes referred to as "additives"). The intermediate layer may contain only the aforementioned non-silicon-based resin, or the aforementioned non-silicon-based resin and the aforementioned additives together.

The aforementioned additives may be any of resin components (in this specification, sometimes referred to as "other resin components") and non-resin components.

As the aforementioned other resin components, for example, non-silicon resins having a weight average molecular weight (Mw) exceeding 100,000 (Mw>100,000) and silicone resins can be cited.

A non-silicone resin with a weight average molecular weight exceeding 100,000 is not particularly limited as long as it satisfies such conditions.

The intermediate layer containing the aforementioned silicon-based resin is as described later, making it easier to pick up the silicon wafer with the film-like adhesive.

The aforementioned silicon-based resin is not particularly limited as long as it is a resin component having silicon atoms as constituent atoms. For example, the weight average molecular weight of the silicone resin is not particularly limited.

As a preferable silicon-based resin, for example, a resin component that exhibits a mold releasing effect on the adhesive component is exemplified, and a silicone-based resin (resin component having a silicone bond (-Si-O-Si-)) is more preferable.

As said silicone resin, polydialkylsiloxane etc. are mentioned, for example. The carbon number of the alkyl group of the aforementioned polydialkylsiloxane is preferably 1-20. In the aforementioned polyalkylsiloxane, the two alkyl groups bonded to one silicon atom may be the same or different from each other. When two alkyl groups bonded to one silicon atom are different from each other, the combination of the two alkyl groups is not particularly limited. As said polydialkylsiloxane, polydimethylsiloxane etc. are mentioned.

The aforementioned non-resin component may be any of an organic compound and an inorganic compound, for example, and is not particularly limited.

The composition for forming the intermediate layer and the aforementioned additives contained in the intermediate layer may be only one type or two or more types. In the case of two or more types, the combination and ratio of these additives can be arbitrarily selected. For example, as the aforementioned additives, the composition for forming the intermediate layer and the intermediate layer may contain one or two or more resin components without non-resin components, or one or two or more non-resin components without resin The components may also contain one or more than two resin components and non-resin components.

When the composition for forming an intermediate layer and the intermediate layer contain the aforementioned additives, the ratio of the content of the aforementioned non-silicon-based resin to the total mass of the intermediate layer in the intermediate layer (in other words, in the composition for forming an intermediate layer, The ratio of the content of the aforementioned non-silicone resin to the total content of all components other than the solvent) is preferably 90% to 99.99% by mass, for example, 90% to 97.5% by mass, 90% to 95% by mass, and Any one of 90% to 92.5% by mass, or any one of 92.5% to 99.99% by mass, 95% to 99.99% by mass, and 97.5% to 99.99% by mass, or 92.5% to 99.99% by mass 97.5 mass%. When the composition for forming the intermediate layer and the intermediate layer contain the aforementioned additives, the ratio of the content of the aforementioned additives in the intermediate layer to the total mass of the intermediate layer (in other words, in the composition for forming the intermediate layer, the ratio of the aforementioned additives The ratio of the content relative to the total content of all ingredients other than the solvent) is preferably 0.01% by mass to 10% by mass, for example, 2.5% by mass to 10% by mass, 5% by mass to 10% by mass, and 7.5% by mass to 10% by mass. Any of% may be any of 0.01% by mass to 7.5% by mass, 0.01% by mass to 5% by mass, and 0.01% by mass to 2.5% by mass, or 2.5% by mass to 7.5% by mass.

The aforementioned solvent contained in the composition for forming an intermediate layer is not particularly limited, but preferred ones include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane -1-ol), 1-butanol and other alcohols; ethyl acetate and other esters; acetone, methyl ethyl ketone and other ketones; tetrahydrofuran and other ethers; dimethylformamide, N-methylpyrrolidone and other amides (Compounds with amide bond) and so on. The solvent contained in the composition for forming an intermediate layer may be only one type or two or more types. In the case of two or more types, the combination and ratio of these solvents can be arbitrarily selected.

The solvent contained in the composition for forming an intermediate layer is preferably tetrahydrofuran or the like in terms of enabling more uniform mixing of the components contained in the composition for forming an intermediate layer.

The content of the solvent in the composition for forming an intermediate layer is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

As will be described later, in terms of making it easier to pick up silicon wafers with a film-like adhesive, a preferable intermediate layer includes, for example, ethylene-vinyl acetate copolymer containing as the aforementioned non-silicon-based resin, and As the aforementioned additive silicone compound, the ratio of the content of the aforementioned ethylene-vinyl acetate copolymer (the aforementioned non-silicone resin) in the intermediate layer to the total mass of the intermediate layer is in any of the aforementioned numerical ranges, and the intermediate layer The ratio of the content of the aforementioned silicone compound (the aforementioned additive) to the total mass of the intermediate layer in any of the aforementioned numerical ranges. For example, as such an intermediate layer, the ethylene-vinyl acetate copolymer containing as the aforementioned non-silicon resin and the silicone compound as the aforementioned additive can be cited, and the aforementioned ethylene-vinyl acetate copolymer in the intermediate layer The ratio of the content relative to the total mass of the intermediate layer is 90% to 99.99% by mass, and the content of the aforementioned silicone compound in the intermediate layer relative to the total mass of the intermediate layer is 0.01% to 10% by mass . However, this is an example of a better intermediate layer.

As a more preferable intermediate layer, for example, the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin and a silicone compound as the additive, in the ethylene-vinyl acetate copolymer , The ratio of the mass of the constituent units derived from vinyl acetate to the total mass of all constituent units (in other words, the content of the constituent units derived from vinyl acetate) is 10% to 40% by mass. In the aforementioned intermediate layer, the aforementioned The ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer is 90% to 99.99% by mass, and the content of the silicone compound in the intermediate layer is relative to the total mass of the intermediate layer The ratio of is 0.01% by mass to 10% by mass. However, this is an example of a better middle layer.

In the semiconductor device manufacturing sheet, the film-like adhesive side surface of the intermediate layer (for example, in Figure 1 When the first surface 13a of the intermediate layer 13 is analyzed, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon (in this specification, sometimes referred to as the ratio of silicon concentration) is preferably It becomes 1% to 20% based on the molar ratio of the element. By using a semiconductor device manufacturing sheet provided with such an intermediate layer, a silicon wafer with a film-like adhesive can be picked up more easily as described later.

XPS analysis uses X-ray photoelectron spectroscopy to set the analysis object as the surface of the film adhesive side of the intermediate layer, set the X-ray irradiation angle to 45°, the X-ray beam diameter to 20μmφ, and output Set to 4.5W and proceed.

The aforementioned silicon concentration ratio can be calculated by the following formula. [Measured value of silicon concentration in XPS analysis (atomic %)]/{[Measured value of carbon concentration in XPS analysis (atomic %)] + [Measured value of oxygen concentration in XPS analysis (atomic %) ] + [Measured value of nitrogen concentration in XPS analysis (atomic %)] + [Measured value of silicon concentration in XPS analysis (atomic %)]}×100.

XPS analysis can use an X-ray photoelectron spectroscopic analysis device (such as "Quantra SXM" manufactured by Ulvac) for the surface of the intermediate layer on the film adhesive side, with an irradiation angle of 45°, an X-ray beam diameter of 20μmφ, Output under the condition of 4.5W.

In terms of this effect becoming more significant, the ratio of the aforementioned silicon concentration may be any of 4% to 20%, 8% to 20%, and 12% to 20% based on the molar basis of the element, for example. It may be any of 1% to 16%, 1% to 12%, and 1% to 8%, or any of 4% to 16% and 8% to 12%.

When performing XPS analysis as described above, it is possible to detect other elements that are not equivalent to any of carbon, oxygen, nitrogen, and silicon on the aforementioned surface of the intermediate layer (the surface to be analyzed by XPS). However, usually even if the aforementioned other elements are detected, the concentration of the other elements is still very small. Therefore, when calculating the ratio of the aforementioned silicon concentration, only the measured values of the concentrations of carbon, oxygen, nitrogen and silicon can be used to calculate the aforementioned with high accuracy. The ratio of silicon concentration.

The intermediate layer may be composed of one layer (single layer), or two or more layers. In the case of being composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

As explained above, the maximum value of the width of the intermediate layer is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the substrate. The maximum width of the intermediate layer can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the intermediate layer can also be 150mm to 160mm, 200mm to 210mm, or 300mm to 310mm. These three numerical ranges correspond to a semiconductor wafer with a maximum width of 150 mm, a maximum width of 200 mm, or a width relative to the direction parallel to the attaching surface of the semiconductor device manufacturing sheet. A semiconductor wafer with a maximum of 300mm. However, as explained above, after the dicing accompanying the formation of the modified layer in the semiconductor wafer, the film-like adhesive is cut by expanding the semiconductor device manufacturing sheet, as described later, the dicing After that, a large number of semiconductor wafers (semiconductor wafer groups) are regarded as a whole, and a semiconductor device manufacturing sheet is attached to these semiconductor wafers.

In this specification, unless otherwise specified, the "width of the intermediate layer" means, for example, the "width of the intermediate layer in a direction parallel to the first surface of the intermediate layer". For example, in the case of an intermediate layer whose planar shape is a circular shape, the maximum value of the width of the aforementioned intermediate layer becomes the diameter of the circle that is the aforementioned planar shape. This situation is the same in the case of semiconductor wafers. That is, the "width of the semiconductor wafer" means the "width of the semiconductor wafer in a direction parallel to the attachment surface of the semiconductor device manufacturing sheet". For example, in the case of a semiconductor wafer whose planar shape is a circular shape, the maximum value of the width of the semiconductor wafer becomes the diameter of the circle that is the planar shape.

The maximum value of the width of the intermediate layer of 150mm to 160mm means that the maximum value of the width of the semiconductor wafer of 150mm is equal to or less than 10mm. Similarly, the maximum value of the width of the intermediate layer of 200mm to 210mm means that the maximum value of the width of the semiconductor wafer of 200mm is equal to or less than 10mm. Similarly, the maximum value of the width of the intermediate layer of 300mm to 310mm means the maximum value of the width of the semiconductor wafer of 300mm is equal to or less than 10mm. That is, in this embodiment, no matter which the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm, the difference between the maximum width of the intermediate layer and the maximum width of the semiconductor wafer may be, for example, 0 mm To 10mm.

The thickness of the intermediate layer can be appropriately selected according to the target, preferably 5 μm to 150 μm, more preferably 5 μm to 120 μm, for example, any of 10 μm to 90 μm and 10 to 60 μm, or 30 μm to 120 μm and 60 μm to 120 μm Any one of. By the thickness of the intermediate layer being above the aforementioned lower limit, the structure of the intermediate layer becomes more stable. When the thickness of the intermediate layer is not more than the aforementioned upper limit, the film-like adhesive can be cut more easily during blade dicing and during the aforementioned expansion of the semiconductor device manufacturing sheet. Here, the "thickness of the intermediate layer" means the thickness of the entire intermediate layer. For example, the thickness of the intermediate layer composed of multiple layers means the total thickness of all the layers constituting the intermediate layer.

When the intermediate layer contains the aforementioned silicon-based resin, especially when the compatibility between the silicone-based resin and the aforementioned non-silicon-based resin as the main component is low, in the semiconductor device manufacturing sheet, the silicon-based resin in the intermediate layer It tends to be concentrated on both sides of the intermediate layer (the first side and the opposite side) and the vicinity thereof. In addition, the stronger this tendency is, the easier it is for the film adhesive adjacent to (directly in contact with) the intermediate layer to peel off from the intermediate layer. As will be described later, the silicon wafer with the film adhesive can be picked up more easily. For example, when comparing interlayers that differ only in thickness from each other but are the same in terms of composition, the area of the aforementioned two surfaces, and other thicknesses, the content of the silicone resin in these interlayers is relative to the total of the interlayers. The mass ratios (mass %) are the same as each other. However, the content (parts by mass) of the silicon-based resin in the intermediate layer is more thick in the intermediate layer than in the thinner intermediate layer. Therefore, when the silicone resin is likely to be concentrated in the intermediate layer as described above, the thick intermediate layer is concentrated on both sides (the first surface and the surface on the opposite side) compared to the thinner intermediate layer. The amount of silicone resin in the nearby area increases. Therefore, even if the aforementioned ratio is not changed, the pick-up suitability of the silicon wafer with the film-like adhesive can be adjusted by adjusting the thickness of the intermediate layer in the semiconductor device manufacturing sheet. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, the silicon wafer with the film-like adhesive can be picked up more easily.

○Film adhesive The aforementioned film-like adhesive has curability, preferably has thermosetting properties, and preferably has pressure-sensitive adhesive properties. The film-like adhesive, which has both thermosetting and pressure-sensitive adhesive properties, can be attached by gently pressing on various adherends in an uncured state. In addition, the film-like adhesive can also be applied to various adherends by being softened by heating. The film adhesive finally becomes a cured product with high impact resistance through curing, and the cured product maintains sufficient adhesive properties even under severe high temperature and high humidity conditions.

When the semiconductor device manufacturing sheet is viewed from above in a plan view, the area of the film-like adhesive (that is, the area of the first surface) is preferably set to be smaller than the area of the semiconductor wafer before division The area of the substrate (that is, the area of the first side) and the area of the adhesive layer (that is, the area of the first side). In such a sheet for manufacturing a semiconductor device, a part of the first surface of the adhesive layer has a region (that is, the aforementioned non-layered region) that is not in contact with the intermediate layer and the film-like adhesive. Thereby, the expansion of the semiconductor device manufacturing sheet becomes easier, and the force applied to the film-like adhesive during expansion is not dispersed, so the film-like adhesive can be cut more easily.

The film adhesive can be formed using an adhesive composition containing the constituent material of the film adhesive. For example, by coating the adhesive composition on the surface to be formed of the film-like adhesive, and drying as necessary, the film-like adhesive can be formed on the target site.

In the film-like adhesive, the ratio of the total content of one or two or more of the film-like adhesive to the total mass of the film-like adhesive to the total mass of the film-like adhesive does not exceed 100% by mass. Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following contained components of the adhesive composition to the total mass of the adhesive composition does not exceed 100% by mass.

The application of the adhesive composition can be performed by the same method as the application of the above-mentioned adhesive composition.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferably heat-dried. In this case, for example, it is preferably dried at 70°C to 130°C for 10 seconds to 5 minutes.

The film adhesive may be composed of one layer (single layer) or multiple layers of two or more layers. In the case of being composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

As explained above, the maximum value of the width of the film adhesive is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the substrate. The maximum width of the film adhesive can be for the size of the semiconductor wafer, which is the same as the maximum width of the intermediate layer described above. That is, the maximum width of the film adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the film adhesive can also be 150 mm to 160 mm, 200 mm to 210 mm, or 300 mm to 310 mm. These three numerical ranges correspond to semiconductor wafers with a maximum width of 150 mm in a direction parallel to the attaching surface of the semiconductor device manufacturing sheet, semiconductor wafers with a maximum width of 200 mm, or width A semiconductor wafer with a maximum of 300mm.

In this specification, unless otherwise specified, the "width of the film adhesive" means, for example, the "width of the film adhesive in a direction parallel to the first surface of the film adhesive". For example, in the case of a film-like adhesive whose planar shape is a circular shape, the maximum width of the film-like adhesive becomes the diameter of the circle that is the planar shape. In addition, unless otherwise specified, the "width of the film-like adhesive" means the "width of the film-like adhesive before cutting (uncut) in the manufacturing process of the semiconductor wafer with the film-like adhesive described later" Width", not the width of the film adhesive after cutting.

The maximum width of the film-like adhesive of 150mm to 160mm means that the maximum width of the semiconductor wafer of 150mm is equal to or less than 10mm. Similarly, the maximum width of the film-like adhesive from 200mm to 210mm means that the maximum width of the 200mm semiconductor wafer is equal to or less than 10mm. Similarly, the maximum width of the film adhesive of 300mm to 310mm means the maximum width of the semiconductor wafer of 300mm is equal to or less than 10mm. That is, in this embodiment, no matter which the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm, the difference between the maximum width of the film adhesive and the maximum width of the semiconductor wafer may be For example, 0mm to 10mm.

In this embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film adhesive can be any of the above numerical ranges. That is, as an example of the semiconductor device manufacturing sheet of this embodiment, the maximum width of the intermediate layer and the maximum width of the film adhesive are both 150mm to 160mm, 200mm to 210mm, or 300mm to 310mm. .

The thickness of the film adhesive is not particularly limited, and is preferably 1 μm to 30 μm, more preferably 2 μm to 20 μm, and particularly preferably 3 μm to 10 μm. When the thickness of the film-like adhesive is greater than the aforementioned lower limit, a higher adhesive force can be obtained with respect to the adherend (semiconductor chip). Since the thickness of the film-like adhesive is below the aforementioned upper limit, the film-like adhesive can be cut more easily at the time of blade dicing or the aforementioned expansion of the semiconductor device manufacturing sheet. Here, the "thickness of the film adhesive" means the thickness of the entire film adhesive. For example, the thickness of the film adhesive composed of multiple layers means the total thickness of all layers constituting the film adhesive. Next, the aforementioned adhesive composition will be described.

[Adhesive composition] As a preferable adhesive composition, for example, it contains a polymer component (a) and a thermosetting component (b). Hereinafter, each component will be explained. In addition, the adhesive composition shown below is a preferable example, and the adhesive composition in this embodiment is not limited to what is shown below.

[Polymer component (a)] The polymer component (a) is regarded as a component formed by the polymerization reaction of a polymerizable compound, and is used to impart film-forming properties or flexibility to the film-like adhesive, and to improve adhesion to semiconductor wafers and other bonding objects (In other words, adhesive) polymer compounds. The polymer component (a) has thermoplasticity and does not have thermosetting properties. In this specification, the polymer compound also includes the product of the polycondensation reaction.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these polymer components (a) Can be chosen arbitrarily.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like. Among these, the polymer component (a) is preferably an acrylic resin.

In the adhesive composition, the ratio of the content of the polymer component (a) to the total content of all components other than the solvent (that is, the content of the polymer component (a) in the film adhesive relative to the film adhesive The ratio of the total mass of the agent) is preferably 20% by mass to 75% by mass, more preferably 30% by mass to 65% by mass.

[Thermosetting component (b)] The thermosetting component (b) is a component that has thermosetting properties and is used to heat-harden the film-like adhesive. The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the thermosetting component (b) is a combination And the ratio can be chosen arbitrarily.

Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

〇Epoxy-based thermosetting resin The epoxy-based thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2). The epoxy-based thermosetting resin contained in the adhesive composition and the film-like adhesive may be one type or two or more types. In the case of two or more types, these epoxy-based thermosetting resins are combined And the ratio can be chosen arbitrarily.

・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, and two Cyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other bifunctional epoxy compounds.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor package obtained by using a film-like adhesive is improved.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these epoxy resins (b1) Can be chosen arbitrarily.

・Thermal hardener (b2) The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1). As the thermosetting agent (b2), for example, a compound having two or more functional groups capable of reacting with epoxy groups in one molecule can be cited. As the aforementioned functional group, for example, phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, acid anhydride group, etc. are mentioned, preferably phenolic hydroxyl group, amino group or acid group anhydride group, more preferably It is a phenolic hydroxyl or amino group.

Among the thermosetting agents (b2), examples of phenolic curing agents having phenolic hydroxyl groups include: polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc. In the thermosetting agent (b2), examples of the amine-based curing agent having an amine group include dicyandiamine (DICY) and the like.

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these thermosetting agents (b2) Can be chosen arbitrarily.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass, more preferably 1 part by mass relative to 100 parts by mass of the epoxy resin (b1). Parts to 200 parts by mass, for example, may be any of 1 part by mass to 100 parts by mass, 1 part by mass to 50 parts by mass, and 1 part by mass to 25 parts by mass. When the aforementioned content of the thermosetting agent (b2) is more than the aforementioned lower limit, it is easier to cure the film-like adhesive. When the aforementioned content of the thermosetting agent (b2) is below the aforementioned upper limit, the moisture absorption rate of the film-like adhesive decreases, and the reliability of the semiconductor package obtained by using the film-like adhesive is further improved.

In the adhesive composition and the film-like adhesive, the content of the thermosetting component (b) relative to the content of the polymer component (a) 100 parts by mass (for example, epoxy resin (b1) and thermosetting agent (b2) The total content of) is preferably 5 parts by mass to 100 parts by mass, more preferably 5 parts by mass to 75 parts by mass, particularly preferably 5 parts by mass to 50 parts by mass, for example, 5 parts by mass to 35 parts by mass and 5 parts by mass Any one of parts by mass to 20 parts by mass. When the aforementioned content of the thermosetting component (b) is in this range, the peeling force between the intermediate layer and the film-like adhesive becomes more stable.

Adhesive composition and film adhesive can also be used to improve various physical properties of the film adhesive, in addition to polymer component (a) and thermosetting component (b), and if necessary, other components that do not correspond to these components Element. Preferred examples of other components contained in the adhesive composition and the film-like adhesive include hardening accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), Energy ray curable resin (g), photopolymerization initiator (h), general additives (i), etc.

[Hardening accelerator (c)] The hardening accelerator (c) is a component used to adjust the hardening speed of the adhesive composition. As a preferable hardening accelerator (c), for example, three grades such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Imidazoles such as 5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one hydrogen atom) Phosphine substituted with organic groups); tetraphenyl borate such as tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl borate, etc.

The hardening accelerator (c) contained in the adhesive composition and the film-like adhesive may be one type or two or more types. In the case of two or more types, the combination and ratio of these hardening accelerators (c) Can be chosen arbitrarily.

In the case of using the hardening accelerator (c), in the adhesive composition and the film-like adhesive, the content of the hardening accelerator (c) is preferably 100 parts by mass relative to the content of the thermosetting component (b) 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the hardening accelerator (c) is more than the aforementioned lower limit, the effect obtained by using the hardening accelerator (c) can be more remarkably obtained. Since the content of the hardening accelerator (c) is below the aforementioned upper limit, for example, the hardening accelerator (c) of high polarity is suppressed in the film-like adhesive under the conditions of high temperature and high humidity to transfer the film-like adhesive and the adherend The adhesion interface side moves and the effect of segregation becomes higher, and the reliability of the semiconductor package obtained by using the film-like adhesive is further improved.

[Filling material (d)] By containing the filler (d), the film-like adhesive further improves the cutting performance of spreading. In addition, by containing the filler (d), the film-like adhesive makes it easier to adjust the thermal expansion coefficient. The thermal expansion coefficient is optimized by the object to be attached to the film-like adhesive, and the semiconductor package obtained by using the film-like adhesive The reliability of the body is further improved. In addition, when the film adhesive contains the filler (d), the moisture absorption rate of the film adhesive after curing can also be reduced, or the heat dissipation can be improved.

The filler (d) may be any one of an organic filler and an inorganic filler, and an inorganic filler is preferred. As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by spheroidizing. 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 filler (d) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these fillers (d) can be arbitrary choose.

When the filler (d) is used, in the adhesive composition, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the filler in the film adhesive ( The ratio of the content of d) to the total mass of the film-like adhesive) is preferably 5 mass% to 80 mass%, more preferably 10 mass% to 70 mass%, and particularly preferably 20 mass% to 60 mass%. When the aforementioned ratio is in such a range, the effect obtained by using the above-mentioned filler (d) can be more remarkably obtained.

[Coupling agent (e)] By containing the coupling agent (e), the film-like adhesive improves the adhesion and adhesion to the adherend. In addition, when the film-like adhesive contains the coupling agent (e), the cured product of the film-like adhesive improves water resistance without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (a) and the thermosetting component (b), and more preferably a silane coupling agent.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these coupling agents (e) may be arbitrary choose.

When the coupling agent (e) is used, in the adhesive composition and the film-like adhesive, the coupling agent (e) is The content of) is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (e) is above the aforementioned lower limit value, the dispersibility of the filler (d) in the resin can be improved significantly, or the adhesion between the film-like adhesive and the adherend can be improved, etc. The effect obtained by using the coupling agent (e). When the aforementioned content of the coupling agent (e) is below the aforementioned upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (f)] When using as the polymer component (a), the acrylic resin, etc., having functional groups such as vinyl, (meth)acrylic, amine, hydroxyl, carboxyl, isocyanate, etc. capable of bonding with other compounds as the polymer component (a), then The agent composition and the film-like adhesive may also contain a crosslinking agent (f). The cross-linking agent (f) is a component used to bond the aforementioned functional groups in the polymer component (a) with other compounds for cross-linking. By such cross-linking, the initial adhesive force of the film-like adhesive can be adjusted and Cohesion.

As the crosslinking agent (f), for example, organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

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 reaction between the crosslinking agent (f) and the polymer component (a) can be easily applied to the film adhesive Import the cross-linked structure.

The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these crosslinking agents (f) Can be chosen arbitrarily.

In the case of using the crosslinking agent (f), in the adhesive composition, the content of the crosslinking agent (f) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer component (a) Parts, more preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 0.3 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is more than the aforementioned lower limit, the effect obtained by using the cross-linking agent (f) can be obtained more remarkably. When the aforementioned content of the cross-linking agent (f) is below the aforementioned upper limit, excessive use of the cross-linking agent (f) is suppressed.

[Energy ray curable resin (g)] Since the adhesive composition and the film-like adhesive contain the energy-ray curable resin (g), the film-like adhesive can change its characteristics by irradiation of energy rays.

The energy ray curable resin (g) is obtained from an energy ray curable compound. As the aforementioned 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 preferred.

The energy ray curable resin (g) contained in the adhesive composition may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable resins (g) may be Free to choose.

In the case of using energy ray curable resin (g), in the adhesive composition, the ratio of the content of the energy ray curable resin (g) to the total mass of the adhesive composition is preferably 1% by mass to 95% % By mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain energy ray curable resin (g), in order to efficiently polymerize the energy ray curable resin (g), a photopolymerization initiator (h ).

The photopolymerization initiator (h) in the adhesive composition includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin Dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenyl Acetophenone compounds such as ethane-1-one; bis(2,4,6-trimethylbenzyl) phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl oxide Phosphine and other phosphine oxide compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyronitrile, etc. Azo compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzophenone; benzophenone; benzophenone; 2 ,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 1-chloroanthracene Quinone, 2-chloroanthraquinone and other quinone compounds. In addition, as the photopolymerization initiator (h), for example, photosensitizers such as amines can also be cited.

The photopolymerization initiator (h) contained in the adhesive composition may be only one type or two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators (h) may be Free to choose.

In the case of using the photopolymerization initiator (h), in the adhesive composition, the content of the photopolymerization initiator (h) is preferably 100 parts by mass relative to the content of the energy ray curable resin (g) 0.1 parts by mass to 20 parts by mass, more preferably 1 parts by mass to 10 parts by mass, particularly preferably 2 parts by mass to 5 parts by mass.

[General additives (i)] The general additives (i) may also be known ones, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred ones include, for example, plasticizers, antistatic agents, antioxidants, and colorants (dyes, pigments) , Getters, etc.

The general additives (i) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these general additives (i) can be arbitrary choose. The content of the adhesive composition and the film-like adhesive is not particularly limited, as long as it is appropriately selected according to the purpose.

[Solvent] The adhesive composition preferably further contains a solvent. The operability of the solvent-containing adhesive composition system becomes better. The aforementioned solvent is not particularly limited. Preferred ones include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1-butanol, etc. 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 and N-methylpyrrolidone (compounds with amide bonds), etc. . The adhesive composition may contain only one solvent, or two or more solvents. In the case of two or more solvents, the combination and ratio of these solvents can be arbitrarily selected.

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

The content of the solvent in the adhesive composition is not particularly limited, and it may be appropriately selected according to the types of components other than the solvent, for example.

[Method of manufacturing adhesive composition] The adhesive composition is obtained by blending the components used to form the adhesive composition. For example, the adhesive composition can be manufactured by the same method as the adhesive composition described above, except for the difference in the types of ingredients.

◇Method of manufacturing semiconductor device manufacturing sheet The aforementioned sheet for manufacturing a semiconductor device can be manufactured by laminating each of the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

For example, the aforementioned semiconductor device manufacturing sheet can be manufactured by preparing a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive in advance, and using these as the substrate, adhesive layer, intermediate layer, and film. The adhesive is laminated in a sequential manner. However, this method is an example of a method of manufacturing a sheet for manufacturing a semiconductor device.

The aforementioned semiconductor device manufacturing sheet may also be manufactured, for example, by pre-preparing two or more intermediate laminates composed of a plurality of laminated layers to constitute the semiconductor device manufacturing sheet, and combining these intermediate laminates with each other To fit together. The structure of the intermediate laminate can be appropriately selected arbitrarily. For example, by prefabricating a first intermediate layered body (corresponding to the aforementioned support sheet) having a structure of laminating a substrate and an adhesive, and a second intermediate layered body having a structure of layering an intermediate layer and a film-like adhesive , And the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate are bonded together to produce a semiconductor device manufacturing sheet. However, this is also an example of a method of manufacturing a sheet for manufacturing a semiconductor device.

As the aforementioned semiconductor device manufacturing sheet, for example, the area of the first surface of the intermediate layer and the area of the first surface of the film adhesive as shown in FIG. 1 are both smaller than the first surface of the adhesive layer and the second surface of the substrate. In the case of the area of one side, it is also possible to add a step of processing the intermediate layer and the film-like adhesive to the target size in any stage of the above-mentioned manufacturing method. For example, in the manufacturing method using the aforementioned second intermediate laminate, a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate to a target size may be additionally performed, thereby manufacturing a semiconductor device manufacturing sheet.

When manufacturing a semiconductor device manufacturing sheet with a release film on the film adhesive, for example, a film adhesive can be prepared on the release film, and the remaining layers can be laminated while maintaining the state to produce a semiconductor device manufacturing sheet ; After the substrate, adhesive layer, intermediate layer and film adhesive are all laminated, a release film can be laminated on the film adhesive to produce a semiconductor device manufacturing sheet. The release film only needs to be removed in a necessary stage before using the semiconductor device manufacturing sheet.

Sheets for manufacturing semiconductor devices with other layers that are not equivalent to any of the base material, adhesive layer, intermediate layer, film-like adhesive, and release film can be formed by adding to the above-mentioned manufacturing method at an appropriate timing The other layers are manufactured by stacking the steps together.

As an example of a preferable semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is sequentially on the aforementioned substrate The adhesive layer, the intermediate layer, and the film adhesive are laminated; the film adhesive contains an antistatic agent, and the ratio of the antistatic agent to the total mass of the film adhesive is 3% by mass Below; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the content of the non-silicon resin is relative to The ratio of the total mass of the aforementioned intermediate layer is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; in the aforementioned intermediate layer, as the aforementioned polar resin The ratio of the content of the non-silicon resin to the total content of the aforementioned non-silicon resin is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; In the polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is any one of 5% to 70% by mass, 7.5 to 55% by mass, and 10% to 40% by mass ; The surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less.

As another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is attached to the aforementioned substrate. The adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated; the film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3 mass % Or less; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains ethylene-vinyl acetate copolymer or polyolefin as the non-silicon resin; the intermediate layer contains at least polar The resin is the aforementioned non-silicon resin; in the intermediate layer, the ratio of the content of the non-silicon resin to the total mass of the intermediate layer is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass Any one of the above and 99% by mass or more; in the intermediate layer, the ratio of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is 80% by mass or more and 90% by mass Any of the above, 95% by mass or more, 97% by mass or more, and 99% by mass or more; in the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all the constituent units is 5 mass% to Any one of 70% by mass, 7.5% by mass to 55% by mass, and 10% by mass to 40% by mass; the surface resistivity of the surface of the intermediate layer side of the film-like adhesive is 1×10 ¹³ Ω or less.

As another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is attached to the aforementioned substrate. The adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated; the film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3 mass % Or less; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin; in the ethylene-vinyl acetate copolymer Among them, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is any one of 10% to 40% by mass, and 10% to 30% by mass. The composition is derived from ethylene The ratio of the mass of the unit to the total mass of all the constituent units is any one of 60% to 90% by mass and 70% to 90% by mass; in the intermediate layer, the content of the ethylene-vinyl acetate copolymer The ratio relative to the total mass of the aforementioned intermediate layer is 90% to 99.99% by mass; the aforementioned intermediate layer contains at least a polar resin as the aforementioned non-silicon resin; in the aforementioned intermediate layer, the content of the aforementioned non-silicon resin is relative to the aforementioned intermediate The ratio of the total mass of the layer is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; in the aforementioned intermediate layer, the aforementioned non-silicone as the aforementioned polar resin The ratio of the content of the resin to the total content of the aforementioned non-silicone resin is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; in the aforementioned polar resin Wherein, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is any one of 5 mass% to 70 mass%, 7.5 mass% to 55 mass%, and 10 mass% to 40 mass%; The surface resistivity of the surface of the intermediate layer side of the film-like adhesive is 1×10 ¹³ Ω or less.

As another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is attached to the aforementioned substrate. The adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated; the film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3 mass % Or less; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component; the intermediate layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the content of the non-silicon resin is relative to The ratio of the total mass in the aforementioned intermediate layer is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; in the aforementioned intermediate layer, as the polar resin The ratio of the content of the aforementioned non-silicone resin to the total content of the aforementioned non-silicone resin is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; In the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is any of 5 mass% to 70 mass%, 7.5% to 55% by mass, and 10 mass% to 40% by mass When analyzing the surface of the film-like adhesive side of the intermediate layer by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon becomes 1% to 20% , 4% to 16% and 8% to 12%; the surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less.

As yet another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is attached to the aforementioned substrate The adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated; the film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3 Mass% or less; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component, and further contains a silicone resin; the intermediate layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the The ratio of the content of the non-silicone resin relative to the total mass of the aforementioned intermediate layer is any of 90% to 99.99% by mass, 90% to 97.5% by mass, 90% to 95% by mass, and 90% to 92.5% by mass One; in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is 0.01% to 10% by mass, 2.5% to 10% by mass, 5% to 10% by mass, and Any one of 7.5 mass% to 10 mass%; wherein, in the aforementioned intermediate layer, the ratio of the total content of the aforementioned non-silicon-based resin and silicone-based resin to the total mass of the aforementioned intermediate layer does not exceed 100% by mass; In the intermediate layer, the ratio of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99 Any one of mass% or more; in the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is 5 mass% to 70 mass%, 7.5% to 55% by mass, and 10 Any one of mass% to 40 mass %; the surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less.

As yet another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the following semiconductor device manufacturing sheet includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and is attached to the aforementioned substrate The adhesive layer, the intermediate layer, and the film adhesive are sequentially laminated; the film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3 Mass% or less; the intermediate layer contains a non-silicon resin with a weight average molecular weight of 100,000 or less as the main component, and further contains a silicone resin; the intermediate layer contains at least a polar resin as the non-silicon resin; in the intermediate layer, the The ratio of the content of the non-silicone resin relative to the total mass of the aforementioned intermediate layer is any of 90% to 99.99% by mass, 90% to 97.5% by mass, 90% to 95% by mass, and 90% to 92.5% by mass One; in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is 0.01% to 10% by mass, 2.5% to 10% by mass, 5% to 10% by mass, and Any one of 7.5 mass% to 10 mass%; wherein, in the aforementioned intermediate layer, the ratio of the total content of the aforementioned non-silicon-based resin and silicone-based resin to the total mass of the aforementioned intermediate layer does not exceed 100% by mass; In the intermediate layer, the ratio of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99 Any one of mass% or more; in the aforementioned polar resin, the ratio of the mass of the constituent unit having a polar group to the total mass of all constituent units is 5 mass% to 70 mass%, 7.5% to 55% by mass, and 10 Any one of mass% to 40% by mass; the thickness of the aforementioned intermediate layer is any one of 5μm to 150μm, 5μm to 120μm, 30μm to 120μm, and 60μm to 120μm; The surface resistivity is 1×10 ¹³ Ω or less.

◇Using method of semiconductor device manufacturing sheet (method of manufacturing semiconductor wafer with film adhesive) The aforementioned sheet for manufacturing a semiconductor device can be used in the manufacturing process of a semiconductor device, when manufacturing a semiconductor wafer with a film-like adhesive. Hereinafter, while referring to the drawings, a method of using the aforementioned semiconductor device manufacturing sheet (a method of manufacturing a semiconductor wafer with a film-like adhesive) will be described in detail.

3A, 3B, and 3C are cross-sectional views for schematically explaining an example of the method of using the semiconductor device manufacturing sheet, and show a state in which the semiconductor device manufacturing sheet is attached to a semiconductor wafer and used. In this method, a semiconductor device manufacturing sheet is used as a dicing die.

The method of manufacturing a semiconductor wafer with a film adhesive of this embodiment includes: step (A1), attaching the inner surface of the semiconductor wafer to the exposed surface of the film adhesive of the semiconductor device manufacturing sheet of the above embodiment , Obtain a laminate composed of the aforementioned substrate, the aforementioned adhesive layer, the aforementioned intermediate layer, the aforementioned film-like adhesive and the aforementioned semiconductor wafer in order; step (A2), the aforementioned semiconductor wafer is divided, and cut Cutting the film adhesive to obtain a semiconductor chip with a film adhesive; and step (A3), pulling off the semiconductor chip with a film adhesive from the substrate, the adhesive layer and the intermediate layer and picking it up. Here, taking the sheet 101 for manufacturing a semiconductor device shown in FIG. 1 as an example, a method of using the sheet 101 for manufacturing a semiconductor device will be described.

First, as shown in FIG. 3A, while heating the semiconductor device manufacturing sheet 101 with the release film 15 removed, the film-like adhesive 14 in the semiconductor device manufacturing sheet 101 is attached to the semiconductor wafer 9 '的内面9b' (Step (A1)). Symbol 9a' denotes the circuit formation surface of the semiconductor wafer 9'.

The heating temperature at the time of attaching the sheet 101 for manufacturing a semiconductor device is not particularly limited, but in terms of further improving the stability of heat attaching of the sheet 101 for manufacturing a semiconductor device, it is preferably 40°C to 70°C.

_{The maximum value of the width W 13} of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 in the semiconductor device manufacturing sheet 101 are exactly the same as the maximum value of the width W _{9 ′ of the semiconductor wafer 9 ′, or} Although they are not the same, the error is slight and basically the same.

_{For example, when the maximum value of the width W 9 ′} of the semiconductor wafer 9 ′ is 150 mm, the maximum value of the width W ₁₃ of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 are preferably 150 mm 160mm to a maximum value, the semiconductor wafer 9 _'9 of a width _W' of 200mm is the case, the intermediate layer is preferably the maximum width W of 13 and a film ₁₃ followed by the maximum value of the width W ₁₄ of the agent 14 is when 200mm to 210mm, the semiconductor wafer 9 _'9 of a width _W' of the case to a maximum of 300mm, the intermediate layer is preferably the maximum width W of 13 and a film ₁₃ followed by the maximum value of the width W ₁₄ of the agent 14 It is 300mm to 310mm. Thus the difference between the maximum value of the present embodiment, the intermediate layer 13 of a width W of the maximum ₁₃ and the semiconductor wafer 9 _'9 of a width _W', the width of the agent and then a film 14 of the semiconductor wafer W with a maximum of ₁₄ the difference between the maximum circle 9 'of the width W is _9' of the can is 0mm to 10mm. Here, the semiconductor wafer 9 'of the width W is _9', for example, a semiconductor wafer means 9 'with respect to the inner surface 9b' as a direction parallel to the width of the.

Next, the laminated product of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9'obtained above is cut with a blade from the circuit forming surface 9a' side of the semiconductor wafer 9'(blade dicing), thereby dividing the semiconductor wafer 9'and cut off the film adhesive 14. (Step (A2)).

The blade cutting can be performed by a known method. For example, the area near the periphery where the intermediate layer 13 and the film-like adhesive 14 are not laminated on the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101 (the aforementioned non-laminated area) can be fixed to the ring frame After waiting for the jig (not shown), the semiconductor wafer 9'is divided and the film adhesive 14 is cut using a blade.

Through this step, as shown in FIG. 3B, a plurality of semiconductor chips 914 with a film-like adhesive can be obtained. The semiconductor chip 914 with a film-like adhesive includes a semiconductor chip 9 and is arranged on the inner surface of the semiconductor chip 9 9b Film adhesive 140 after cutting. These semiconductor wafers 914 with a film-like adhesive are in a state of being neatly arranged and fixed on the intermediate layer 13 of the laminated sheet 10, forming a group of semiconductor wafers 910 with a film-like adhesive. The inner surface 9b of the semiconductor wafer 9 corresponds to the inner surface 9b' of the semiconductor wafer 9'. In addition, in FIG. 3B, reference numeral 9a denotes the circuit formation surface of the semiconductor wafer 9 and corresponds to the circuit formation surface 9a' of the semiconductor wafer 9'.

When cutting with a blade, it is preferable to use a blade to divide the semiconductor wafer 9'by cutting into the entire thickness direction, and for the semiconductor device manufacturing sheet 101, it is cut from the first surface 14a of the film-like adhesive 14 to As far as the midway region of the intermediate layer 13 is reached, the film-like adhesive 14 is cut in the entire thickness direction by this, and the adhesive layer 12 is not cut. That is, when cutting with a blade, it is preferable to use a blade. For the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9', at least cut into the circuit formation surface 9a' of the semiconductor wafer 9'in the layering direction Up to the first surface 13a of the intermediate layer 13 and not cut to the surface of the intermediate layer 13 opposite to the first surface 13a (that is, the contact surface with the adhesive layer 12).

In this step, it is possible to prevent the blade from reaching the base material 11 so easily, thereby suppressing the generation of cutting chips from the base material 11. In addition, the main component of the intermediate layer 13 cut by the blade is a non-silicone resin with a weight average molecular weight of 100,000 or less, especially a weight average molecular weight of 100,000 or less, thereby also suppressing the generation of cutting chips from the intermediate layer 13.

The conditions for blade cutting are not particularly limited as long as they are appropriately adjusted according to the purpose. Generally, the rotating speed of the blade is preferably 15000 rpm to 50000 rpm, and the moving speed of the blade is preferably 5 mm/s to 75 mm/s.

After the blade is diced, as shown in FIG. 3C, the semiconductor wafer 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminated sheet 10 and picked up (step (A3)). Here, it is shown that the semiconductor wafer 914 with the film-like adhesive is pulled away in the direction of arrow P using the pull-off mechanism 7 such as a vacuum collet. Furthermore, the section of the pull-off mechanism 7 is shown here. The semiconductor chip 914 with the film-like adhesive can be picked up by a known method.

On the first surface 13a of the intermediate layer 13, when the aforementioned silicon concentration ratio is 1% to 20%, the semiconductor wafer 914 with the film-like adhesive can be picked up more easily. The intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer as the aforementioned non-silicon resin and a silicone compound as the aforementioned additive. The content of the ethylene-vinyl acetate copolymer in the intermediate layer is relative to that of the intermediate layer. When the ratio of the total mass is 90% to 99.99% by mass, and the ratio of the content of the aforementioned silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass, it can be easier Groundly pick up the semiconductor wafer 914 with the film-like adhesive.

Among the methods of manufacturing a semiconductor wafer with a film-like adhesive described so far, as a preferred embodiment, for example, the following method of manufacturing a semiconductor wafer with a film-like adhesive can be cited. The semiconductor wafer includes a semiconductor wafer and a film adhesive provided on the inner surface of the semiconductor wafer, and the semiconductor device manufacturing sheet includes the substrate, an adhesive layer, an intermediate layer, and a film adhesive; the manufacturing method has The following steps: a step of attaching the film adhesive in the semiconductor device manufacturing sheet to the inner surface of the semiconductor wafer while heating the semiconductor device manufacturing sheet; attaching the film adhesive The semiconductor wafer of the agent is cut into the entire thickness direction from the circuit forming surface side to be divided to produce the semiconductor wafer, and the semiconductor device manufacturing sheet is cut in the thickness direction from the film-like adhesive side to the intermediate layer Cut the film-like adhesive until the midway area of, and not cut into the adhesive layer, thereby obtaining a film-like state in which a plurality of semiconductor wafers with the film-like adhesive are arranged neatly on the intermediate layer The step of the semiconductor wafer group of the adhesive; and the step of pulling the semiconductor wafer with the film-like adhesive from the intermediate layer and picking it up (in this specification, it is sometimes referred to as "manufacturing method 1").

4A, 4B, and 4C are cross-sectional views for schematically explaining an example of a method of manufacturing a semiconductor wafer used as a semiconductor device manufacturing sheet, showing the formation of a modified layer accompanying the semiconductor wafer Cutting and manufacturing semiconductor wafers. 5A, FIG. 5B, and FIG. 5C are cross-sectional views schematically illustrating another example of the method of using the semiconductor device manufacturing sheet, showing a situation in which the semiconductor device manufacturing sheet is attached to a semiconductor chip and used. In this method, a sheet for manufacturing a semiconductor device is used as a bonding wafer.

The method of manufacturing a semiconductor wafer with a film adhesive of this embodiment includes: step (B1) of attaching a plurality of the semiconductor wafers to the exposed surface of the film adhesive of the semiconductor device manufacturing sheet of the above embodiment The inner surface of the semiconductor chip group in a neatly arranged state obtains a laminate composed of the substrate, the adhesive layer, the intermediate layer, the film adhesive, and the semiconductor chip group in order; step (B2) ), cutting the aforementioned film-like adhesive to obtain a semiconductor chip with a film-like adhesive; and step (B3), pulling away from the aforementioned substrate, the aforementioned adhesive layer and the aforementioned intermediate layer from the aforementioned film-like adhesive Semiconductor wafers are picked up. Here, taking the sheet 101 for manufacturing a semiconductor device shown in FIG. 1 as an example, a method of using the sheet 101 for manufacturing a semiconductor device will be described.

First, before using the semiconductor device manufacturing sheet 101, as shown in FIG. 4A, a semiconductor wafer 9'is prepared, and a back polishing tape (sometimes also referred to as " Surface protection tape”) 8. 4A, the symbols W is _{9 'of} a semiconductor wafer 9' width.

Then, the laser light (not shown) is irradiated so as to be focused to a focal point set inside the semiconductor wafer 9', thereby forming a modified layer 90' inside the semiconductor wafer 9'as shown in FIG. 4B. The aforementioned laser light is preferably irradiated to the semiconductor wafer 9'from the inner surface 9b' side of the semiconductor wafer 9'.

The position of the focus at this time is the predetermined position for dividing (cutting) the semiconductor wafer 9', which is set in such a way that the semiconductor wafer 9'obtains the target size, shape, and number of semiconductor chips.

Then, a grinder (not shown) is used to grind the inner surface 9b' of the semiconductor wafer 9'. Thereby, the thickness of the semiconductor wafer 9'is adjusted to the target value, and the semiconductor wafer 9 is divided at the formation portion of the modified layer 90' by using the force applied to the semiconductor wafer 9'at the time of grinding ', a plurality of semiconductor wafers 9 are produced as shown in FIG. 4C.

The modified layer 90' of the semiconductor wafer 9'is different from other parts of the semiconductor wafer 9', and is deteriorated by the irradiation of laser light, and its strength becomes weaker. Therefore, by applying force to the semiconductor wafer 9'on which the modified layer 90' is formed, and applying force to the modified layer 90', the semiconductor wafer 9'is broken at the portion of the modified layer 90', and more A semiconductor wafer 9.

Through the above operations, the semiconductor wafer 9 to be used of the semiconductor device manufacturing sheet 101 is obtained. More specifically, through this step, a semiconductor wafer group 901 in a state where a plurality of semiconductor wafers 9 are aligned and fixed on the back polishing tape 8 is obtained.

When the semiconductor wafer group 901 is viewed from above and viewed in a plan view, the outermost part of the semiconductor wafer group 901 is connected to form a planar shape (in this specification, this planar shape is sometimes referred to as "semiconductor wafer group" Plane shape") is exactly the same as the planar shape of the semiconductor wafer 9'when viewed from above, or the difference between these planar shapes is slight to negligible degree, and it can be said that the aforementioned planar shape of the semiconductor wafer group 901 is the same as that of the semiconductor wafer. The aforementioned planar shape of the circle 9'is substantially the same. Thus, the width of the flat shape of the semiconductor wafer group 901 is shown in FIG. 4C, the semiconductor wafer 9 is regarded as 'the width W is _9' same. Moreover, the maximum value of the width of the aforementioned planar shape of the semiconductor wafer group 901 is regarded as the same as the maximum value _{of the width W 9 ′ of the semiconductor wafer 9 ′.}

Furthermore, here is shown the case where the semiconductor wafer 9 is made from the semiconductor wafer 9'according to the purpose. However, depending on the conditions during the grinding of the inner surface 9b' of the semiconductor wafer 9', it may also be used on the semiconductor wafer. The semiconductor wafer 9 is not divided into a part of the region 9'.

Then, the semiconductor wafer 9 (semiconductor wafer group 901) obtained above is used to manufacture a semiconductor wafer with a film-like adhesive. First, as shown in FIG. 5A, while heating one sheet 101 for manufacturing a semiconductor device with the release film 15 removed, the film-like adhesive 14 in the sheet 101 for manufacturing a semiconductor device is attached to the semiconductor wafer group 901. All the semiconductor wafers 9 in the inner surface 9b (step (B1)). At this time, the attachment target of the film-like adhesive 14 may also be an incompletely divided semiconductor wafer.

_{The maximum value of the width W 13} of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film adhesive 14 in the semiconductor device manufacturing sheet 101 are the same as the width W _{9'of the semiconductor wafer 9'} (in other words, the semiconductor chip group 901 The maximum value of the width) is exactly the same, or it is different but the error is slight and basically the same.

Width i.e., the intermediate layer 13 of width W and the relationship between the maximum value of the maximum width ₁₃ of the semiconductor wafer 901 with the group described above, the intermediate layer 13 of a width W of the maximum ₁₃ and the semiconductor wafer 9 'of the the same relationship to the maximum value W _{9 'of.} Furthermore, the relationship between a film and then the maximum value of the width W of the maximum width of the agent 14 of the semiconductor wafer ₁₄ of the group 901 may be a film as described above, then the agent 14 of a width W between the maximum and the semiconductor wafer ₉₁₄ the same relationship to the maximum value 'of the width W _9' of.

At this time, the film-like adhesive 14 (semiconductor device manufacturing sheet 101) is attached to the semiconductor wafer group 901 in addition to the semiconductor wafer group 901 instead of the semiconductor wafer 9'. The film-like adhesive 14 (sheet 101 for manufacturing a semiconductor device) was attached to the circle 9'by the same method.

Then, the back polishing tape 8 is removed from the semiconductor wafer group 901 in the fixed state. Then, as shown in FIG. 5B, while cooling the semiconductor device manufacturing sheet 101, it is pulled in a direction parallel to the surface of the semiconductor device manufacturing sheet 101 (for example, the first surface 12a of the adhesive layer 12). Stretch, and expand with this. Here, an arrow E ₁ for manufacturing a semiconductor device 101 of the extension direction of the sheet. By expanding in this way, the film-like adhesive 14 is cut along the outer periphery of the semiconductor wafer 9 (step (B2)).

Through this step, a plurality of semiconductor wafers 914 with a film-like adhesive can be obtained. The plurality of semiconductor wafers 914 with a film-like adhesive are provided with a semiconductor chip 9 and disposed on the inner surface 9b of the semiconductor chip 9 after being cut. The film adhesive 140. These semiconductor wafers 914 with a film-like adhesive are in a state of being neatly arranged and fixed on the intermediate layer 13 of the laminated sheet 10, forming a group of semiconductor wafers 910 with a film-like adhesive. The semiconductor chip 914 with a film-like adhesive and the semiconductor chip group 910 with a film-like adhesive obtained here are the same as the semiconductor chip 914 with a film-like adhesive and a film obtained by the manufacturing method 1 described above. The semiconductor chip group 910 of the adhesive agent is substantially the same.

As described above, when the semiconductor wafer 9'is divided, when a part of the semiconductor wafer 9'is not divided into semiconductor wafers 9 in a partial area, the area is divided into semiconductor wafers by performing this step.

The sheet 101 for manufacturing a semiconductor device is preferably expanded at a temperature of -5°C to 5°C. By cooling and expanding the sheet 101 for manufacturing a semiconductor device in this way (cold expansion), the film-like adhesive 14 can be cut more easily and with high precision.

The expansion of the semiconductor device manufacturing wafer 101 can be performed by a known method. For example, fix the area near the periphery of the adhesive layer 12 on the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are not laminated (the aforementioned non-laminated area) to a ring frame, etc. After the jig (not shown), the entire area of the semiconductor device manufacturing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are laminated is topped from the substrate 11 in the direction from the substrate 11 to the adhesive layer 12 Therefore, the semiconductor device manufacturing sheet 101 can be expanded by this.

In FIG. 5B, in the first surface 12a of the adhesive layer 12, the aforementioned non-laminated area where the intermediate layer 13 and the film-like adhesive 14 are not laminated is approximately parallel to the first surface 13a of the intermediate layer 13, but as described above As described above, in the state expanded by the lifting of the semiconductor device manufacturing sheet 101, the aforementioned non-laminated area includes an inclined surface, and the height of the inclined surface is opposite to the above-mentioned lifting direction as it approaches the outer periphery of the adhesive layer 12 The direction is down.

In this step, the sheet 101 for manufacturing a semiconductor device is provided with the intermediate layer 13 (in other words, the film-like adhesive 14 before cutting is provided on the intermediate layer 13), and the film-like adhesive 14 is placed on the target portion (in other words, along the (The outer periphery of the semiconductor wafer 9) is cut with high accuracy, and cutting failures can be suppressed.

After the expansion, as shown in FIG. 5C, the semiconductor wafer 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminated sheet 10 and picked up (step (B3)). The pick-up at this time can be performed by the same method as the pick-up in the manufacturing method 1 described above, and the pick-up adaptability is also the same as the pick-up adaptability in the manufacturing method 1.

For example, in this step, even when the ratio of the aforementioned silicon concentration on the first surface 13a of the intermediate layer 13 is 1% to 20%, the semiconductor wafer 914 with the film-like adhesive can be picked up more easily. In addition, the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer as the aforementioned non-silicon resin and a silicone compound as the aforementioned additive. The content of the ethylene-vinyl acetate copolymer in the intermediate layer is relative to that of the intermediate layer. When the ratio of the total mass of the layer is 90% to 99.99% by mass, and the ratio of the content of the aforementioned silicone compound in the intermediate layer to the total mass of the intermediate layer is 0.01% to 10% by mass, It is easier to pick up the semiconductor wafer 914 with the film-like adhesive.

Among the methods of manufacturing a semiconductor wafer with a film-like adhesive described so far, as a preferred embodiment, for example, the following method for manufacturing a semiconductor wafer with a film-like adhesive can be cited. The semiconductor wafer is provided with a semiconductor wafer and a film-like adhesive provided on the inner surface of the aforementioned semiconductor wafer, and the aforementioned semiconductor device manufacturing sheet is provided with the aforementioned base material, an adhesive layer, an intermediate layer, and a film-like adhesive; and The method includes the following steps: forming a modified layer inside the semiconductor wafer by irradiating laser light to a focal point set inside the semiconductor wafer; and forming the modified layer after the modified layer is formed. The inner surface of the semiconductor wafer is ground, and by using the force applied to the semiconductor wafer during grinding, the semiconductor wafer is divided at the formation portion of the modified layer to obtain a plurality of the semiconductor wafers in an orderly arrangement The step of the semiconductor wafer group in the state; while heating the semiconductor device manufacturing sheet, the film-like adhesive in the semiconductor device manufacturing sheet is attached to the inner surfaces of all the semiconductor wafers in the semiconductor wafer group The step; while cooling the sheet for manufacturing a semiconductor device after being attached to the semiconductor wafer, it is stretched in a direction parallel to the surface of the sheet for manufacturing a semiconductor device, thereby bonding the film The agent is cut along the outer periphery of the semiconductor wafer to obtain a group of semiconductor wafers with a film adhesive in a state where the semiconductor wafers with a film adhesive are neatly arranged on the intermediate layer; and from the middle The step of separating and picking up the aforementioned semiconductor wafer with the film-like adhesive (in this specification, it is sometimes referred to as "manufacturing method 2").

So far, in any of the manufacturing method 1 and the manufacturing method 2, the semiconductor device manufacturing sheet 101 shown in FIG. 1 is taken as an example to describe the usage method. However, the semiconductor device manufacturing of the present embodiment is other than this. The tablets can also be used in the same way. In this case, other steps may be appropriately added based on the difference between the configuration of the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101 as necessary, and the semiconductor device manufacturing sheet may be used.

It is not limited to the case of manufacturing method 1 and manufacturing method 2. After obtaining the semiconductor chip group with the film-like adhesive, before picking up the semiconductor chip with the film-like adhesive, the laminated sheet may be attached to the adhesive The surface (first surface) on the side of the intermediate layer of the agent layer expands in a parallel direction, and then maintains this state, and the semiconductor wafer with the film-like adhesive is not placed on the laminated sheet (the film-like adhesive) The peripheral part of the semiconductor wafer group) is heated. By setting in this way, the peripheral portion can be shrunk, and the distance between adjacent semiconductor wafers, that is, the kerf width, is sufficiently wide and uniform on the laminate sheet to be maintained. Moreover, it is easier to pick up semiconductor wafers with a film-like adhesive. [Example]

Hereinafter, the present invention will be described in more detail through specific embodiments. However, the present invention is not limited at all by the examples shown below.

[Materials for manufacturing adhesive composition] The raw materials used to manufacture the adhesive composition are shown below. [Polymer component (a)] (a)-1: Acrylic resin (weight average molecular weight 800,000, glass transition temperature 9°C) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass). [Epoxy resin (b1)] (b1)-1: Cresol novolac epoxy resin with acryl group added ("CNA147" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518g/eq, number average molecular weight 2100, and unsaturated group content Epoxy equivalent). [Thermal Hardener (b2)] (b2)-1: Aralkyl phenol resin (Milex XLC-4L manufactured by Mitsui Chemicals Co., Ltd., number average molecular weight 1100, softening point 63°C) [Filling material (d)] (d)-1: Spherical silicon dioxide ("YA050C-MJE" manufactured by Admatechs, with an average particle size of 50nm, treated with methacrylic acid silane) [Coupling agent (e)] (e)-1: Silane coupling agent, 3-glycidoxypropylmethyl diethoxysilane ("KBE-402" manufactured by Shin-Etsu Polysiloxane) [Crosslinking agent (f)] (f)-1: Toluene diisocyanate-based crosslinking agent ("Coronate L" manufactured by Tosoh) [Antistatic agent (g)] (g)-1: Reduced graphene oxide (“N002-PDR” manufactured by Angstrom Material Company)

[Example 1] [Manufacturing of sheets for semiconductor device manufacturing] [Manufacturing of base material] Use an extruder to melt low-density polyethylene (LDPE, "Sumikasen L705" manufactured by Sumitomo Chemical Co., Ltd.), extrude the melt by the T-die method, and stretch the extrudate on a biaxial axis using a cooling roll to obtain Base material made of LDPE (thickness 110μm).

[Making of Adhesive Layer] Manufacture of a non-energy-ray-curable adhesive composition containing acrylic resin ("Oribain BPS 6367X" manufactured by Toyo-Chem) as an adhesive resin (I-1a) ") (100 parts by mass), and a crosslinking agent ("BXX 5640" manufactured by Toyo-Chem) (1 part by mass).

Then, using a peeling film on one side of a polyethylene terephthalate film that has been peeled off by a silicone treatment, the adhesive composition obtained above is coated on the peeling surface, and heated and dried at 100°C for 2 minutes , To produce a non-energy-ray curable adhesive layer (thickness 10μm).

[Production of Intermediate Layer] At room temperature, ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 30,000, content of constituent units derived from vinyl acetate 25% by mass) (15g) was dissolved in 85g of tetrahydrofuran, and the resultant Add siloxane compound (polydimethylsiloxane, BYK Chemie Japan, "BYK-333" manufactured by BYK Chemie Japan), with the formula "-Si(-CH ₃ ) _2- The number of structural units indicated by "O-" is 45 to 230) (1.5 g), which is stirred to produce a composition for forming an intermediate layer.

Using a polyethylene terephthalate film with a peeling film on one side that has been peeled off by a silicone treatment, apply the above-obtained composition for forming an intermediate layer on the peeling surface, and heat and dry at 70°C for 5 minutes , Thereby fabricating an intermediate layer (thickness 20 μm).

[Production of Film Adhesive] Manufacture a thermosetting adhesive composition containing polymer component (a)-1 (100 parts by mass), epoxy resin (b1)-1 (10 parts by mass), and thermosetting Agent (b2)-1 (1.5 parts by mass), filler (d)-1 (75 parts by mass), coupling agent (e)-1 (0.5 parts by mass), crosslinking agent (f)-1 (0.5 parts by mass) ) And antistatic agent (g)-1 (5.6 parts by mass).

Then, using a peeling film on one side of a polyethylene terephthalate film that has been peeled off by a silicone treatment, the adhesive composition obtained above is coated on the peeling surface, and heated and dried at 80°C for 2 minutes , To produce a thermosetting film-like adhesive (thickness 7μm).

[Manufacturing of sheets for semiconductor device manufacturing] The exposed surface of the adhesive layer obtained above, which is opposite to the side with the release film, is bonded to one surface of the substrate obtained above to produce a first intermediate laminate having a release film (in other words, Support sheet with peeling film). The exposed surface of the film-like adhesive obtained above that is opposite to the side with the release film is bonded to the exposed surface of the intermediate layer obtained above that is the side opposite to the side with the release film, thereby making a tool The second intermediate laminate of the release film (the laminate of the release film, the intermediate layer, the film-like adhesive, and the release film).

Then, with respect to the second intermediate laminate with a release film, a cutting knife was used to press the release film on the intermediate layer side to the film-like adhesive to remove unnecessary parts, thereby producing a second intermediate laminate with a release film Processed product, the second intermediate laminate processed product with a release film is attached to the release film on the side of the film-shaped adhesive, and the film-shaped adhesive (thickness 7μm) with a circular planar shape (diameter 305mm) and an intermediate layer ( (Thickness 20μm) and the release film are laminated in the thickness direction in this order.

Then, the release film is removed from the first intermediate laminate with release film obtained above, so that one side of the adhesive layer is exposed. Furthermore, the round peeling film was removed from the second intermediate laminate processing product with a peeling film obtained above, so that one side of the intermediate layer was exposed.

Then, the newly formed exposed surface of the adhesive layer in the first intermediate layered body and the newly formed exposed surface of the intermediate layer in the second intermediate layered body are bonded together. Regarding the substrate and adhesive layer (ie, support sheet) in the laminate obtained by this, the planar shape of these layers is circular (305mm in diameter), and it is combined with the circular film-like adhesive and intermediate layer. The concentric method uses a cutting knife to press from the side of the substrate to remove useless parts.

Through the above operations, the sheet for manufacturing a semiconductor device with a release film of Example 1 is obtained. The sheet for manufacturing a semiconductor device with a release film of Example 1 is composed of a substrate (thickness 110 μm) and an adhesive layer (thickness 10 μm). ), an intermediate layer (thickness 20 μm), a film-like adhesive (thickness 7 μm), and a release film are laminated in the thickness direction of these in this order.

[Evaluation of Semiconductor Device Manufacturing Sheets] [Measurement of the surface resistivity of the surface of the intermediate layer side of the film adhesive] The peeling film in the obtained sheet for manufacturing a semiconductor device with a peeling film was peeled off, and the entire exposed surface of the film-like adhesive produced thereby was attached to an adhesive tape having a polyethylene terephthalate layer ("PET50(A) PL thin 8LK" manufactured by Lintec), the adhesive surface is cut into 100mm×100mm to make a test piece. After adjusting the humidity of the test piece at 23°C and 50% relative humidity for 24 hours, peel off the test piece at the interface between the intermediate layer and the film adhesive. At 23°C and 50% relative humidity, use DIGITAL ELECTROMETER (manufactured by ADVANTEST) ) Measure the surface resistivity of the exposed surface of the film adhesive at an applied voltage of 100V.

[Calculation of the ratio of the silicon concentration in the film-like adhesive side surface of the intermediate layer] In the manufacturing process of the above-mentioned semiconductor device manufacturing sheet, the exposed surface of the intermediate layer at the stage before bonding with the adhesive layer was analyzed by XPS to determine carbon (C), oxygen (O), and nitrogen (N) And the concentration of silicon (Si) (atomic %), the ratio (%) of the concentration of silicon relative to the total concentration of carbon, oxygen, nitrogen and silicon is calculated based on the measured value. XPS analysis was performed using an X-ray photoelectron spectroscopic analyzer ("Quantra SXM" manufactured by Ulvac) under the conditions of an irradiation angle of 45°, an X-ray beam diameter of 20μmφ, and an output of 4.5W. Show the result and the ratio (%) of the concentration of other elements in the column of "The ratio of the element concentration of the intermediate layer (%)" in Table 1.

[Evaluation of the effect of suppressing cutting chips during cutting of the blade] [Manufacturing of silicon chip group with film adhesive] In the semiconductor device manufacturing sheet obtained above, the release film was removed. Use a silicon wafer (diameter 300mm, thickness 75μm) whose inner surface has been dry-polished and polished. On the inner surface (polished surface) of the silicon wafer, use a tape machine (Lintec company "Adwill RAD2500"), while heating the above-mentioned sheet for manufacturing a semiconductor device to 60°C, it is attached with the film-like adhesive of the sheet for manufacturing a semiconductor device. In this way, the substrate (thickness 110μm), the adhesive layer (thickness 10μm), the intermediate layer (thickness 20μm), the film adhesive (thickness 7μm) and the silicon wafer (thickness 75μm) are obtained sequentially in the thickness direction of these A layered product formed by layering (a layered product formed by sequentially layering the aforementioned layered sheet, film-like adhesive, and silicon wafer in the thickness direction of these).

Then, the area near the peripheral edge portion (the aforementioned non-layered area) on the first surface of the adhesive layer in the laminate that is not provided with the intermediate layer is fixed to the ring frame for wafer dicing. Then, a dicing device ("DFD6361" manufactured by Disco) was used to cut the silicon wafer, and the film-like adhesive was also cut to obtain a silicon wafer with a size of 8mm×8mm. The cutting at this time is carried out by the following method: the rotation speed of the blade is set to 30,000 rpm, and the moving speed of the blade is set to 30 mm/s. For the semiconductor device manufacturing sheet, the blade is used to adhere from the film of the semiconductor device manufacturing sheet The silicon wafer attaching surface of the agent is cut to the midway area of the intermediate layer (that is, the entire area in the thickness direction of the film adhesive, and the intermediate layer from the surface on the film adhesive side to the midway area ). As the blade, "Z05-SD2000-D1-90 CC" manufactured by Disco was used. Through the above operations, a group of silicon wafers with a film-like adhesive is obtained in the following state: one of a plurality of film-like adhesives with a silicon wafer and a film-like adhesive disposed on the inner surface of the silicon wafer after cutting The silicon wafers are aligned and fixed on the intermediate layer of the aforementioned laminated sheet by means of a film-like adhesive.

[Evaluation of the effect of suppressing the generation of cutting chips] Using a digital microscope (“VH-Z100” manufactured by Keyence Corporation), observe the group of silicon wafers with a film-like adhesive obtained above from the upper side of the silicon wafer to confirm whether cutting chips are generated. In addition, it is judged as "A" when no chips are generated at all, and it is judged as "B" when chips are generated even though it is a little. The results are shown in Table 1.

[Evaluation of the cutting performance of the film adhesive during expansion] [Manufacturing of silicon wafer group with film adhesive] A silicon wafer with a circular planar shape, a diameter of 300 mm, and a thickness of 775 μm is used, and a back polishing tape (“Adwill E-3100TN” manufactured by Lintec Corporation) is attached to one side of the silicon wafer. Then, a laser light irradiation device ("DFL73161" manufactured by Disco) was used to irradiate the laser light to a focal point set inside the silicon wafer, thereby forming a change in the inside of the silicon wafer. Quality layer. At this time, the aforementioned focus is set in such a way that a plurality of silicon wafers with a size of 8mm×8mm are obtained from the silicon wafer. In addition, the laser beam irradiates the silicon wafer from the other side (the side on which the back grinding tape is not attached). Then, use a grinder to grind the other side of the silicon wafer, thereby adjusting the thickness of the silicon wafer to 30μm, and by using the force applied to the silicon wafer during grinding, The silicon wafer is divided into sections where the modified layer is formed to produce multiple silicon wafers. Thereby, a group of silicon wafers in a state where a plurality of silicon wafers are neatly arranged and fixed on the back polishing belt is obtained.

Then, using a tape sticking machine ("Adwill RAD2500" manufactured by Lintec Corporation), one of the semiconductor device manufacturing sheets obtained above was heated to 60°C while the film-like shape in the semiconductor device manufacturing sheet was heated. The adhesive is attached to the other surface (in other words, the grinding surface) of all the silicon wafers (silicon wafer group). Then, the area near the peripheral edge of the adhesive layer on the first surface of the semiconductor device manufacturing sheet attached to the silicon wafer group where the intermediate layer is not provided (the aforementioned non-layered area) is fixed to the wafer dicing ring frame.

Then, the back polishing tape is removed from the silicon wafer group in the fixed state. Then, using a fully automatic die separator ("DDS2300" manufactured by Disco), the semiconductor device manufacturing sheet was cooled at a temperature of 0°C, while being oriented relative to the surface of the semiconductor device manufacturing sheet. Expand in a parallel direction, thereby cutting the film-like adhesive along the periphery of the silicon wafer. At this time, by fixing the peripheral edge of the semiconductor device manufacturing sheet, the entire region of the semiconductor device manufacturing sheet where the intermediate layer and the film-like adhesive are laminated is raised from the base material side by a height of 15 mm to expand. Thereby, a group of silicon wafers with a film-like adhesive in the following state is obtained: one of a plurality of film-like adhesives with a silicon wafer and a cut-off film-like adhesive provided on the other surface (grinding surface) The silicon wafers are neatly arranged and fixed on the middle layer.

Then, after temporarily releasing the expansion of the above-mentioned semiconductor device manufacturing sheet, at room temperature, the substrate, the adhesive layer, and the intermediate layer are laminated to form a laminate (that is, the aforementioned laminate sheet) relative to the adhesive layer. The first side is expanded in a parallel direction. Furthermore, while maintaining this expanded state, the peripheral part of the semiconductor wafer with a film-like adhesive which is not mounted in the said laminated sheet is heated. As a result, the peripheral edge portion is contracted, and the width of the cut between adjacent silicon wafers on the laminate sheet is maintained at a certain value or more.

[Evaluation of cutting performance of film adhesive] In the manufacture of the above-mentioned silicon wafer group with a film-like adhesive, a digital microscope (“VH-Z100” manufactured by Keyence Corporation) was used to compare the above-mentioned silicon wafer group with a film-like adhesive from silicon Observe the upper side of the wafer side. In addition, confirm the number of the following cutting lines, and evaluate the cutting properties of the film adhesive according to the following evaluation criteria. The above cutting lines assume that the film adhesive is normal by the expansion of the semiconductor device manufacturing sheet In the case of cutting, the cutting lines of a plurality of film adhesives extending in one direction and the cutting lines of a plurality of film adhesives extending in a direction orthogonal to the direction must be formed. Incomplete cut lines and incomplete cut lines. The results are shown in Table 1. [Evaluation criteria] A: The total number of the cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is not completely formed is 5 or less. B: The total number of cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is not completely formed is 6 or more.

[Evaluation of the pick-up of expanded silicon wafer with film adhesive] After evaluating the cutting performance of the above-mentioned film-like adhesive, a silicon wafer group with a film-like adhesive and a die-bonding device ("PU100" manufactured by Fasford Technology) were used to lift up the height of 250μm and the top The pick-up speed is 5mm/s, and the pick-up time is 500ms. The silicon wafer with the film-like adhesive is picked up from the middle layer of the aforementioned laminated sheet. Moreover, it is evaluated as "A" when all silicon wafers with film adhesive can be picked up normally, and "B" when it is impossible to pick up more than one silicon wafers with film adhesive normally. The results are shown in Table 1.

[Measurement of T peel strength between the intermediate layer and the film adhesive] In the semiconductor device manufacturing sheet obtained above, the release film was removed. The whole surface of the exposed surface of the film-like adhesive in the sheet for manufacturing semiconductor devices thus produced was attached to an adhesive tape having a polyethylene terephthalate layer (manufactured by Lintec) The adhesive surface of PET50(A) PL thin 8LK”) is cut out with a size of 50mm×100mm to make a test piece. In this test piece, according to JIS K6854-3, the laminate of the base material, the adhesive layer and the intermediate layer (that is, the laminate sheet), the laminate of the film-like adhesive and the adhesive tape are torn apart, thereby making the test The sheet was peeled off in a T-shape, and the maximum peel force (mN/50mm) measured at this time was used as the T-shape peel strength. At this time, the peeling speed was set to 50 mm/min. The results are shown in Table 1.

[Reliability Evaluation of Semiconductor Package in Chip/Chip Form] [Production of silicon chip group with film adhesive (1)] For the mirror surface of silicon wafer (8inch, thickness 720μm), use a tape bonding device ("RAD3510" manufactured by Lintec) to bond the back polishing tape (made by Lintec) at room temperature. ADWILL E-3125KN”) adhesive surface.

Then, a grinder ("DGP8760" manufactured by Disco) was used to grind (dry polishing) from the inner surface of the silicon wafer, thereby adjusting the thickness of the silicon wafer to 75 μm.

Then, the release film in the semiconductor device manufacturing sheet with release film is peeled off, and the exposed surface of the film-like adhesive produced by this is removed using a laminating device ("VA-400" manufactured by Daesei Laminator Co., Ltd.) It is attached to the polished surface of a silicon wafer (8inch, 75μm thick) that has been dry-polished. The bonding is performed under the conditions of 40°C, lamination speed: 0.6m/min, and 0.5MPa. In this way, the base material (thickness 110μm), the adhesive layer (thickness 10μm), the intermediate layer (thickness 20μm), the film adhesive (thickness 7μm), the silicon wafer (thickness 75μm) and the back polishing tape were obtained in this order. A layered structure (1) formed by laminating these in the thickness direction (a layered structure (1) formed by sequentially layering the aforementioned layered sheet, film adhesive, silicon wafer, and back polishing tape in the thickness direction of these )).

Then, the obtained laminated structure (1) was attached to and fixed to a ring frame for dicing, and the back polishing tape attached to the mirror side of the wafer was peeled off.

Then, using a dicing device ("DFD6361" manufactured by Disco Co., Ltd.), the silicon wafer was divided at 50 mm/s and 40,000 rpm, and the film-like adhesive was also cut to obtain a size of 8mm×8mm. Wafer. The cutting amount at the time of cutting was set to be 20 μm from the side of the film-like adhesive layer to the intermediate layer of the aforementioned laminated sheet. Through the above steps, a group of silicon wafers (1) with a film-like adhesive for reliability evaluation of semiconductor packages in the following state is obtained: the silicon wafer is provided with the inner surface of the silicon wafer after being cut A plurality of silicon wafers with a film-like adhesive of the film-like adhesive are fixedly arranged and fixed on the intermediate layer of the aforementioned laminated sheet by the film-like adhesive.

[Production of Silicon Chip Group (2) with Adhesive Layer] The aforementioned semiconductor device manufacturing sheet composed of a substrate, an adhesive layer, an intermediate layer, a film-like adhesive, and a release film was changed to a commercially available dicing composed of a substrate, an adhesive layer (thickness 20 μm), and a release film Except for the bonding wafer (manufactured by Lintec, Adwill LE5729S), the substrate, adhesive layer (thickness 20μm) and silicon crystal A layered structure (2) composed of a circle (thickness 75μm) and a back polishing tape layered in the thickness direction of these in order.

Then, the obtained laminated structure (2) was attached to and fixed to a ring frame for dicing, and the back polishing tape attached to the mirror side of the wafer was peeled off.

Then, using a dicing device ("DFD6361" manufactured by Disco Co., Ltd.), the silicon wafer was divided at 50mm/s and 40,000rpm, and the adhesive layer was also cut to obtain a silicon wafer with a size of 8mm×8mm . The cutting amount during cutting is set to cut into the substrate 20 μm. Through the above steps, a group of silicon wafers with an adhesive layer (2) for reliability evaluation of semiconductor packages in the following state is obtained: a silicon wafer is provided, and the adhesive layer is cut and disposed on the inner surface of the silicon wafer A plurality of silicon wafers with an adhesive layer of the agent layer are fixedly arranged and fixed on the middle layer of the aforementioned laminated sheet through the adhesive layer.

[Reliability Evaluation of Semiconductor Package in Chip/Chip Form] As the substrate, a copper-clad laminate ("HL832NX-A" manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a circuit pattern formed on copper foil (thickness 18μm) and solder resist (made by Sun Ink Co., Ltd.) is used as the substrate. PSR-4000AUS308") substrate ("LN001E-001 PCB(Au)AUS308" manufactured by Zhimo Electronics Co., Ltd.).

Pick up the silicon wafer with the adhesive layer from the silicon wafer group (2) with the adhesive layer for reliability evaluation of the semiconductor package. On the aforementioned substrate, the aforementioned silicon wafer with the adhesive layer was crimped through the adhesive layer under the conditions of 120°C, 2.45N (250gf), 0.5 seconds, and the silicon wafer was fixed on the substrate by the adhesive layer to obtain A laminate of the aforementioned substrate and silicon wafer with adhesive layer.

Then, an oven was used to heat the obtained laminate of the aforementioned substrate and the silicon wafer with the adhesive layer at 160° C. for 1 hour. Then, the aforementioned layered product was taken out from the oven and cooled to normal temperature.

Pick up a silicon wafer with a film adhesive from the group (1) of silicon wafers with a film adhesive for reliability evaluation of semiconductor packages. On the silicon wafer of the laminate cooled to room temperature, the silicon wafer with the film-like adhesive was crimped at 120°C, 2.45N (250gf), 0.5 seconds, and heated in an oven at 160°C for 1 hour . Then, it was taken out from the oven, and the aforementioned layered product was cooled to normal temperature. Using a sealing device ("MPC-06M TriAl Press" manufactured by Apic Yamada), the sealing resin ("KE-1100AS3" manufactured by Kyocera Chemical Co., Ltd.) was applied to the chip with a thickness of 400μm After the upper sealing, it is heated at 175°C for 5 hours to harden the aforementioned sealing resin.

Then, the sealed laminate was attached to a cutting tape ("Adwill D-510T" manufactured by Lintec), using a cutting device ("DFD6361" manufactured by Disco Co., Ltd.), The sealing resin film with a thickness of 1mm left around the side of the silicon wafer of 8mm×8mm was cut into a size of 10mm×10mm to obtain a semiconductor package for reliability evaluation.

Place the semiconductor package in the form of a wafer/wafer with a semiconductor wafer layered on the semiconductor wafer obtained above at a temperature of 85°C and a relative humidity of 60% for 168 hours to absorb moisture (JEDEC Level 2). Then, using a desktop reflow oven ("STR-2010N2M" manufactured by Senju Metal Industry Co., Ltd.), the semiconductor package after moisture absorption was subjected to 3 times of IR reflow under the conditions of a maximum temperature of 260°C and a heating time of 1 minute. Then, using an ultrasonic microscope ("D-9600" manufactured by Sonoscan), for 9 semiconductor packages, the semiconductor packages were laminated on the semiconductor chips to evaluate whether there were cracks, And whether the wafers/wafers bonded by the film-like adhesives of the examples have swelling and peeling are evaluated as reliability. The results are shown in Table 1.

In addition, in Table 1, the description of "9/9", for example, means that in the evaluation of 9 semiconductor packages, there was no semiconductor package in which bumps, peeling, or cracks were observed. The description of "8/9" means that in the evaluation of 9 semiconductor packages, no bumps, peeling or cracks were observed in 8 semiconductor packages, and bumps, peeling or packages were observed in the aforementioned joints in 1 package. The occurrence of cracks.

[Manufacturing and Evaluation of Sheets for Semiconductor Device Manufacturing] [Example 2] In the production of the film adhesive, 5.6 parts by mass (2.9% by mass) of the aforementioned antistatic agent was changed to 0.95 parts by mass (0.5% by mass) in the adhesive composition. Except for adding the aforementioned siloxane-based compound to the composition for layer formation, a semiconductor device manufacturing sheet was manufactured by the same method as in Example 1, and evaluated. The results are shown in Table 1. The description of "-" in the column of additives in Table 1 means that the additives are not used.

[Example 3] During the production of the intermediate layer, the silicone compound is not added to the composition for forming the intermediate layer, and the content of the constituent units derived from vinyl acetate of the ethylene-vinyl acetate copolymer is changed to 25% by mass Except for 40% by mass, a sheet for manufacturing a semiconductor device was manufactured by the same method as in the case of Example 1, and evaluated. The results are shown in Table 1. The description of "-" in the column of additives in Table 1 means that the additives are not used.

[Example 4] During the production of the intermediate layer, the silicone compound was not added to the composition for forming the intermediate layer, and the weight average molecular weight of the ethylene-vinyl acetate copolymer was changed from 30,000 to 200,000. In addition to this, use and the examples The semiconductor device manufacturing wafer was manufactured and evaluated in the same way as in the case of 1. The results are shown in Table 1. The description of "-" in the column of additives in Table 1 means that the additives are not used.

[Comparative Example 1] Except that the intermediate layer was not provided, a semiconductor device manufacturing sheet was manufactured by the same method as in the case of Example 1, and evaluated. The results are shown in Table 2. The description of "-" in the column of additives in Table 2 means that no intermediate layer is provided.

[Reference example 1] In the production of the film-like adhesive, 5.6 parts by mass (2.9% by mass) of the aforementioned antistatic agent was changed to 7.9 parts by mass (4.0% by mass) in the adhesive composition. During the production of the intermediate layer, it was not used in the intermediate layer. Except for adding the aforementioned siloxane-based compound to the forming composition, a semiconductor device manufacturing sheet was manufactured by the same method as in Example 1, and evaluated. The results are shown in Table 2. The description of "-" in the column of additives in Table 2 means that the additives are not used.

[Reference example 2] When the film adhesive is made, the aforementioned antistatic agent is not added to the adhesive composition, and when the intermediate layer is made, the aforementioned silicone compound is not added to the composition for forming the intermediate layer. , The semiconductor device manufacturing sheet was manufactured by the same method as in the case of Example 1, and evaluated. The results are shown in Table 2. The description of "-" in the column of additives in Table 2 means that the additives are not used.

[Table 1] Example 1 Example 2 Example 3 Example 4 Antistatic agent content of film adhesive (mass%) 2.9 0.5 2.9 2.9 The composition of the middle layer main ingredient Ingredient name EVA EVA EVA EVA Weight average molecular weight 30000 30000 30000 200000 Content (mass%) 90.9 100 100 100 Vinyl acetate (mass%) 25 25 40 25 additive Ingredient name Polydimethylsiloxane - - - Content (mass%) 9.1 - - - Thickness (μm) 20 20 20 20 Evaluation results Surface resistivity (Ω) 7.0E+12 8.0E+12 7.0E+12 7.0E+12 The ratio of element concentration in the middle layer (%) C 66 81 70 81 O 25 19 30 19 N 0 0 0 0 Si 9 0 0 0 The effect of suppressing the generation of cutting chips when the blade is cutting A A A A The cutting performance of the film-like adhesive during expansion A A A A Pickup of silicon chip with film adhesive A B B B T peel strength between the intermediate layer and the film adhesive (mN/50mm) 100 200 400 200 Package reliability evaluation (good/n number) 9 of 9 9 of 9 9 of 9 9 of 9

[Table 2] Comparative example 1 Reference example 2 Reference example 3 Antistatic agent content of film adhesive (mass%) 2.9 4.0 0 The composition of the middle layer main ingredient Ingredient name - EVA EVA Weight average molecular weight - 30000 30000 Content (mass%) - 100 100 Vinyl acetate (mass%) - 25 40 additive Ingredient name - - - Content (mass%) - - - Thickness (μm) - 20 20 Evaluation results Surface resistivity (Ω) 2.0E+13 4.0E+11 ＞1.0E+14 The ratio of element concentration in the middle layer (%) C - 81 81 O - 19 19 N - 0 0 Si - 0 0 The effect of suppressing the generation of cutting chips when the blade is cutting B A A The cutting performance of the film-like adhesive during expansion B A A Pickup of silicon chip with film adhesive B B B T peel strength between the intermediate layer and the film adhesive (mN/50mm) - 200 200 Package reliability evaluation (good/n number) 9 of 9 8 of 9 9 of 9

As shown by the above results, in Examples 1 to 4, the generation of cutting chips during blade dicing is suppressed, while the film-like adhesive is prevented from cutting defects during expansion, and the splitting suitability of semiconductor wafers is excellent . In Examples 1 to 4, the surface resistivity of the surface of the intermediate layer side of the film-like adhesive is 1×10 ¹³ Ω or less. destroy. In Examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as the main component of the intermediate layer in the sheet for manufacturing a semiconductor device was 30,000. In Example 4, the weight average molecular weight of the ethylene-vinyl acetate copolymer was 200,000.

Furthermore, in Examples 1 to 4, in the intermediate layer, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer is 90% by mass or more, and the silicone compound The ratio of the content to the total mass of the aforementioned intermediate layer is 10% by mass or less.

In addition, in Example 1, the expanded silicon wafer with a film-like adhesive has excellent pick-up properties. In Example 1, the T-peel strength between the intermediate layer and the film-like adhesive was lower than 100 mN/50 mm, which was moderately lower, and the silicon concentration ratio of the intermediate layer was 9%, which was moderately higher. These evaluation results match the evaluation results of the pick-up properties of the silicon wafer with the film-like adhesive described above. In Examples 2 to 4, the intermediate layer in the semiconductor device manufacturing sheet did not contain the aforementioned siloxane-based compound.

Furthermore, in Examples 1 to 4, when the exposed surface of the intermediate layer was subjected to XPS analysis, nitrogen was not detected.

In Examples 1 to 4, the semiconductor package in the form of a wafer/wafer in which a semiconductor wafer is further laminated on the semiconductor wafer has excellent reliability.

In contrast, in Comparative Example 1, the generation of cutting chips during blade dicing was not suppressed, and the suitability for dividing the semiconductor wafer was poor. In Reference Example 1 to Reference Example 2, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as the main component in the intermediate layer in the sheet for manufacturing a semiconductor device was 30,000.

In Reference Example 1, the surface resistivity is small, and it can be expected that it can prevent the generation of static electricity or the resulting charging of semiconductor wafers and the like and the destruction of the circuit. However, in Reference Example 1, the ratio of the content of the antistatic agent to the total mass of the film adhesive exceeded 3% by mass, and the adhesive performance of the film adhesive was impaired. As a result, the reliability of the semiconductor package in the form of a chip/wafer was poor. . In Reference Example 2, the surface resistivity is high, and there is a possibility of static electricity generation.

In addition, in Reference Example 1 to Reference Example 2, when XPS analysis was performed on the exposed surface of the intermediate layer, nitrogen was not detected. [Industry Availability]

The present invention can be used to manufacture semiconductor devices.

1: Support sheet 7: Pull-off mechanism 8: Back grinding tape 9: Semiconductor wafer 9': Semiconductor wafer 9a: Circuit formation surface of semiconductor wafer 9a': Circuit formation surface of semiconductor wafer 9b: Inner surface of semiconductor wafer 9b ': the inner surface of the semiconductor wafer 10: the laminate sheet 11: the base material 11a: the first surface of the base material 12: the adhesive layer 12a: the surface of the adhesive layer opposite to the side on which the base material is provided (adhesive The first surface of the agent layer) 13: Intermediate layer 13a: The surface of the intermediate layer on the opposite side to the side where the adhesive layer is provided (the first surface of the intermediate layer) 14: Film-like adhesive 14a: Film-like adhesive The first side 15: peeling film 90': modified layer 101: semiconductor device manufacturing sheet 140: film-shaped adhesive after cutting 901: semiconductor wafer group 910: semiconductor wafer group with film-shaped adhesive 914: film the semiconductor wafer-like adhesive ₁ of E: Expanding the direction P: the tear-off direction W _{9 ':} a width W of the semiconductor wafer _{13 is:} the width W of the intermediate layer _14: film-like agents of Subsequently width

Fig. 1 is a cross-sectional view schematically showing a sheet for manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 2] A plan view of the semiconductor device manufacturing sheet shown in Fig. 1. [Fig. [FIG. 3A] is a cross-sectional view for schematically explaining an example of a method of using a sheet for manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 3B] is a cross-sectional view for schematically explaining an example of the method of using the sheet for manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 3C] is a cross-sectional view for schematically explaining an example of a method of using the sheet for manufacturing a semiconductor device according to an embodiment of the present invention. [FIG. 4A] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor wafer. [FIG. 4B] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor wafer. [FIG. 4C] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor wafer. [FIG. 5A] is a cross-sectional view schematically illustrating another example of the method of using the semiconductor device manufacturing sheet according to an embodiment of the present invention. [FIG. 5B] is a cross-sectional view for schematically explaining another example of the method of using the semiconductor device manufacturing sheet according to an embodiment of the present invention. [FIG. 5C] is a cross-sectional view schematically illustrating another example of the method of using the semiconductor device manufacturing sheet according to an embodiment of the present invention.

1: Support piece

10: Multilayer film

11: Substrate

11a: The first side of the substrate

12: Adhesive layer

12a: The surface of the adhesive layer opposite to the side where the substrate is provided (the first surface of the adhesive layer)

13: middle layer

13a: The side of the intermediate layer that is opposite to the side where the adhesive layer is provided (the first side of the intermediate layer)

14: Film adhesive

14a: The first side of the film adhesive

15: Peel off the film

101: Sheets for semiconductor device manufacturing

W ₁₃ : the width of the middle layer

W ₁₄ : Width of film adhesive

Claims (7)

A sheet for manufacturing semiconductor devices, comprising a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive; the adhesive layer, the intermediate layer, and the film-like adhesive are sequentially laminated on the substrate; The film adhesive contains an antistatic agent, and the ratio of the content of the antistatic agent to the total mass of the film adhesive is 3% by mass or less; the intermediate layer contains a non-silicone resin with a weight average molecular weight of 100,000 or less as Main component: The surface resistivity of the surface of the intermediate layer side of the film adhesive is 1×10 ¹³ Ω or less. The semiconductor device manufacturing sheet according to claim 1, wherein when the surface of the intermediate layer on the film adhesive side is analyzed by X-ray photoelectron spectroscopy, the concentration of silicon is relative to carbon, oxygen, nitrogen, and The ratio of the total concentration of silicon becomes 1% to 20%. The semiconductor device manufacturing sheet according to claim 1 or 2, wherein the intermediate layer contains an ethylene-vinyl acetate copolymer or polyolefin as the non-silicon resin. The semiconductor device manufacturing sheet according to claim 3, wherein the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin; In the aforementioned ethylene-vinyl acetate copolymer, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 10% by mass to 40% by mass. The semiconductor device manufacturing sheet according to claim 4, wherein the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin and a silicone-based compound; In the aforementioned intermediate layer, the ratio of the content of the aforementioned ethylene-vinyl acetate copolymer to the total mass of the aforementioned intermediate layer is 90% to 99.99% by mass; In the intermediate layer, the ratio of the content of the silicone compound to the total mass of the intermediate layer is 0.01% to 10% by mass. A method for manufacturing a semiconductor wafer with a film-like adhesive includes the following steps: Attach the inner surface of the semiconductor wafer to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet described in any one of claims 1 to 5, and obtain the substrate, the adhesive layer, and the intermediate The step of layering, the film-like adhesive, and the semiconductor wafer in order to form a laminate; The step of dividing the aforementioned semiconductor wafer and cutting the aforementioned film-like adhesive to obtain a semiconductor wafer with the film-like adhesive; The step of pulling off the semiconductor wafer with the film-like adhesive from the substrate, the adhesive layer and the intermediate layer and picking it up. A method for manufacturing a semiconductor wafer with a film-like adhesive includes the following steps: On the exposed surface of the film-like adhesive of the sheet for manufacturing a semiconductor device as described in any one of claims 1 to 5, attach the inner surface of a semiconductor wafer group in which a plurality of the semiconductor wafers are arranged neatly to obtain The step of stacking a laminate composed of the aforementioned substrate, the aforementioned adhesive layer, the aforementioned intermediate layer, the aforementioned film-like adhesive, and the aforementioned semiconductor chip group in sequence; The step of cutting the aforementioned film-like adhesive to obtain a semiconductor wafer with the film-like adhesive; and The step of pulling off the semiconductor wafer with the film-like adhesive from the substrate, the adhesive layer and the intermediate layer and picking it up.

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