CN114586141A - Sheet for manufacturing semiconductor device - Google Patents

Abstract

The present invention is a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer, and a film-like adhesive, wherein the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the base material, and the intermediate layer contains a non-silicon resin having a weight-average molecular weight of 100000 or less as a main component.

Description

Sheet for manufacturing semiconductor device

Technical Field

The present invention relates to a sheet for manufacturing a semiconductor device.

The present application claims priority based on Japanese patent application No. 2020 and 058734 filed in Japan on 27.3.2020, and the contents thereof are incorporated herein by reference.

Background

In the manufacture of a semiconductor device, a semiconductor chip with a film-like adhesive is used which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.

As an example of a method for manufacturing a semiconductor chip with a film-like adhesive, the following method can be mentioned.

That is, first, a dicing die bonding sheet (dicing die bonding sheet) is attached to the back surface of the semiconductor wafer.

As the dicing solid wafer, for example, there is exemplified a dicing solid wafer having a support sheet and a film-like adhesive provided on one surface of the support sheet, and the support sheet can be used as a dicing sheet. As the support sheet, there are a plurality of support sheets having different structures, for example, a support sheet including a base material and an adhesive layer provided on one surface of the base material; a support sheet composed only of a base material, and the like. The support sheet provided with the adhesive layer has an outermost surface on the adhesive layer side as a surface on which the film-like adhesive is provided. The dicing die is attached to the back surface of the semiconductor wafer through the film-like adhesive therein.

Subsequently, the semiconductor wafer on the support sheet is cut together with the film-like adhesive by dicing with a blade. The "cutting" of the semiconductor wafer is also referred to as "dicing", and thus the semiconductor wafer is singulated (divided) into semiconductor chips. The film-like adhesive is cut along the outer periphery of the semiconductor chip. Thus, a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip after cutting, can be obtained, and a semiconductor chip group with a film-like adhesive, which is configured such that a plurality of semiconductor chips with a film-like adhesive are held in an aligned state on a support sheet, can be obtained at the same time.

Then, the semiconductor chip with the film-like adhesive is pulled away from the support sheet to be picked up. When a support sheet having a curable adhesive layer is used, the adhesive layer is cured in advance to reduce the adhesiveness, and thus the sheet can be picked up more easily.

Thus, a semiconductor chip with a film-like adhesive for manufacturing a semiconductor device can be obtained.

As another example of a method for manufacturing a semiconductor chip with a film-like adhesive, the following method can be mentioned.

That is, first, a back-grinding tape (also referred to as a "surface-protecting tape") is attached to the circuit-formed surface of the semiconductor wafer.

Then, a portion to be divided is set in the semiconductor wafer, and a laser beam is irradiated so as to focus on a region included in the portion, thereby forming a modified layer in the semiconductor wafer. Then, the back surface of the semiconductor wafer is polished by a grinder (grinder) to adjust the thickness of the semiconductor wafer to a target value, and the semiconductor wafer is divided (singulated) at a portion where the modified layer is formed by a force applied to the semiconductor wafer at the time of polishing, thereby producing a plurality of semiconductor chips. Such a method of dividing a semiconductor wafer with formation of a modified layer is called Stealth Dicing (registered trademark), which is fundamentally completely different from laser Dicing in which a semiconductor wafer is cut from the surface of the semiconductor wafer while the semiconductor wafer at an irradiated portion is cut by irradiating the semiconductor wafer with a laser beam.

Then, one fixed wafer is attached to the back surface (in other words, the polished surface) of all the semiconductor chips fixed to the back-grinding tape, which has been polished as described above. The solid wafer may be the same sheet as the above-described diced solid wafer. As described above, the solid wafer may sometimes be designed to have the same structure as the diced solid wafer, but is not used when dicing the semiconductor wafer. The die bond sheet may be attached to the back surface of the semiconductor chip by a film-like adhesive in the die bond sheet.

Next, after removing the back-grinding tape from the semiconductor chip, the fixed wafer is stretched in a direction parallel to the surface thereof (for example, the surface to which the film-like adhesive is attached to the semiconductor chip) while being cooled, and is subjected to so-called spreading (cold spreading), whereby the film-like adhesive is cut along the outer periphery of the semiconductor chip.

Thus, a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip after cutting, can be obtained.

Next, in the same manner as in the case of the above-described dicing with a blade, the semiconductor chip with the film-like adhesive is pulled away from the support sheet to be picked up, whereby the semiconductor chip with the film-like adhesive for manufacturing a semiconductor device can be obtained.

Both the dicing die and the die bonding sheet can be used for manufacturing a semiconductor chip with a film adhesive, and a desired semiconductor device can be finally manufactured. In this specification, the diced solid-state wafer and the solid-state wafer are collectively referred to as a "semiconductor device manufacturing wafer".

As a sheet for manufacturing a semiconductor device, for example, a dicing die bonding tape (corresponding to the dicing die bonding sheet) having a structure in which a base material layer (corresponding to the support sheet) and an adhesive layer (corresponding to the film-like adhesive) are laminated so as to be in direct contact with each other is disclosed (see patent document 1). In the dicing die-bonding tape, since the 90-degree peel force at-15 ℃ of the base layer and the adhesive layer is adjusted to a specific range, the adhesive layer can be cut with good precision by spreading, and since the 90-degree peel force at 23 ℃ of the base layer and the adhesive layer is adjusted to a specific range, when the dicing die-bonding tape is used, the semiconductor chip with the adhesive layer (corresponding to the semiconductor chip with the film-like adhesive) can be picked up without difficulty, and the semiconductor wafer and the semiconductor chip can be prevented from being peeled from the adhesive layer until the picking up.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-56289

Disclosure of Invention

Technical problem to be solved by the invention

However, the Dicing die bonding tape disclosed in patent document 1 is suitable for application to Stealth Dicing (registered trademark), but is not suitable for application to blade Dicing. When the dicing tape is used for dicing, Whisker-like cutting chips (also referred to as "Whisker (Whisker)" in this field) are likely to be generated from the base material layer, and the dicing suitability for dicing semiconductor wafers is poor.

The purpose of the present invention is to provide a semiconductor device manufacturing sheet having excellent suitability for dividing a semiconductor wafer.

Means for solving the problems

The present invention provides a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer, and a film-like adhesive, wherein the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the base material, and the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component.

In the semiconductor device manufacturing sheet of the present invention, when the surface of the intermediate layer on the film-like binder side is analyzed by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon may be 1 to 20%.

In the semiconductor device-manufacturing sheet of the present invention, the intermediate layer contains an ethylene vinyl acetate copolymer and a siloxane compound as the non-silicone resin, the ratio of the mass of a structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene vinyl acetate copolymer may be 10 to 40% by mass, the ratio of the content of the ethylene vinyl acetate copolymer to the total mass of the intermediate layer in the intermediate layer may be 90 to 99.99% by mass, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer may be 0.01 to 10% by mass.

Effects of the invention

According to the present invention, a semiconductor device manufacturing sheet having excellent suitability for dividing a semiconductor wafer can be provided.

Drawings

Fig. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention.

Fig. 2 is a plan view of the semiconductor device manufacturing sheet shown in fig. 1.

Fig. 3A is a cross-sectional view schematically illustrating an example of a method of using a semiconductor device manufacturing sheet according to an embodiment of the present invention.

Fig. 3B is a cross-sectional view schematically illustrating an example of a method of using a semiconductor device manufacturing sheet according to an embodiment of the present invention.

Fig. 3C is a cross-sectional view schematically illustrating an example of a method of using a 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 for manufacturing a semiconductor chip.

Fig. 4B is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip.

Fig. 4C is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip.

Fig. 5A is a cross-sectional view schematically illustrating another example of a method of using a semiconductor device manufacturing sheet according to an embodiment of the present invention.

Fig. 5B is a cross-sectional view schematically illustrating another example of a method of using a sheet for manufacturing a semiconductor device according to an embodiment of the present invention.

Fig. 5C is a sectional view schematically illustrating another example of a method for using the semiconductor device manufacturing sheet according to the embodiment of the present invention.

Detailed Description

Wafer for manufacturing semiconductor device

The sheet for manufacturing a semiconductor device according to one embodiment of the present invention includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive, and is configured by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the base material, wherein the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component.

When the semiconductor device-manufacturing sheet of the present embodiment is used as a dicing die-bonding sheet and subjected to dicing, since the semiconductor device-manufacturing sheet includes the intermediate layer, it is possible to easily avoid the blade from reaching the base material, and to suppress the generation of Whisker-like cutting chips (also known as Whisker (hereinafter, not limited to only cutting chips derived from the base material, but also simply referred to as "cutting chips") derived from the base material. Further, by making the main component of the intermediate layer cut by the blade a non-silicone resin having a weight average molecular weight of 100000 or less, particularly by making the weight average molecular weight of 100000 or less, it is possible to suppress the generation of the cutting chips from the intermediate layer.

On the other hand, when Dicing (Stealth Dicing (registered trademark)) accompanied by formation of a modified layer in a semiconductor wafer is performed using the semiconductor device manufacturing sheet of the present embodiment as a die bonding sheet, the semiconductor device manufacturing sheet including the intermediate layer can be stretched, i.e., spread, in a direction parallel to the surface thereof (for example, the surface to which the film-shaped adhesive is attached to the semiconductor chip) by continuing to stretch the semiconductor device manufacturing sheet, and cut the film-shaped adhesive at a target position with good accuracy, thereby suppressing a cutting failure.

As described above, the sheet for manufacturing a semiconductor device according to the present embodiment can suppress the generation of chips from the base material and the intermediate layer when dicing the semiconductor wafer, can suppress the cutting failure of the film-like adhesive when spreading the sheet, has a characteristic of suppressing the occurrence of failure when dividing the semiconductor wafer, and has excellent suitability for dividing the semiconductor wafer.

In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

Hereinafter, a method of using the semiconductor device manufacturing sheet of the present embodiment will be described in detail.

Hereinafter, the semiconductor device manufacturing sheet according to the present embodiment will be described in detail with reference to the drawings. For convenience, important parts in the drawings used in the following description are enlarged and shown in order to facilitate understanding of the features of the present invention, and the dimensional ratios of the respective components are not necessarily the same as the actual ones.

Fig. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention, and fig. 2 is a plan view of the semiconductor device manufacturing sheet shown in fig. 1.

In the drawings subsequent to fig. 2, the same reference numerals as those in the already-described drawings are assigned to the same components as those shown in the already-described drawings, and detailed description thereof is omitted.

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

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

The semiconductor device manufacturing sheet 101 is used in the following manner: in the state where the release film 15 is removed, the first surface 14a of the film-like adhesive 14 in the semiconductor device manufacturing sheet 101 is bonded to the back surface of a semiconductor wafer, a semiconductor chip, or a semiconductor wafer (not shown) which is not completely divided.

In the present specification, in both the semiconductor wafer and the semiconductor chip, a surface on which a circuit is formed is referred to as a "circuit forming surface", and a surface opposite to the circuit forming surface is referred to as a "back surface".

In the present specification, a laminate having a structure in which a base material and an adhesive layer are laminated in the thickness direction thereof and an intermediate layer is not laminated is sometimes referred to as a "support sheet". In fig. 1, reference numeral 1 denotes a support sheet.

A laminate having a structure in which a substrate, an adhesive layer, and an intermediate layer are sequentially laminated in the thickness direction thereof is referred to as a "laminate sheet". The laminate is designated by reference numeral 10 in figure 1. The laminate of the support sheet and the intermediate layer is contained in the laminate sheet.

When the intermediate layer 13 and the film-like adhesive 14 are viewed from above the intermediate layer 13 and the film-like adhesive 14 in a plan view, the planar shapes of the intermediate layer 13 and the film-like adhesive 14 are both circular, and the diameter of the intermediate layer 13 is the same as the diameter of the film-like adhesive 14.

In the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 are arranged so that the centers thereof coincide with each other, in other words, so that the outer circumferential positions of the intermediate layer 13 and the film-like adhesive 14 coincide with each other in the radial direction thereof.

The first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 are smaller in area than the first surface 12a of the adhesive layer 12. And the width W of the intermediate layer 13₁₃Maximum value (i.e., diameter) of (d) and width W of film-like adhesive 14₁₄Are smaller than the maximum value of the width of the adhesive layer 12 and the maximum value of the width of the base material 11. Therefore, in the semiconductor device manufacturing sheet 101, a part of the first surface 12a of the adhesive layer 12 is not covered with the intermediate layer 13 and the film-like adhesive 14. The release film 15 is laminated on such a region of the first surface 12a of the adhesive agent layer 12 where the intermediate layer 13 and the film-like adhesive 14 are not laminated, in direct contact therewith, and this region is exposed in a state where the release film 15 is removed (hereinafter, this region may be referred to as a "non-laminated region" in the present specification).

In the semiconductor device manufacturing sheet 101 including the release film 15, as described herein, a region where the release film 15 is not laminated may be present on a region of the adhesive layer 12 not covered with the intermediate layer 13 and the film-like adhesive 14, or a region where the release film 15 is not laminated may be absent.

The semiconductor device manufacturing sheet 101 in a state where the film-like adhesive 14 is not cut and is attached to the semiconductor wafer, the semiconductor chip, or the like by the film-like adhesive 14 can be fixed by attaching a part of the non-lamination region in the adhesive layer 12 to a jig such as a ring frame for fixing the semiconductor wafer. Therefore, it is not necessary to separately provide an adhesive layer for a jig on the semiconductor device manufacturing sheet 101 for fixing the semiconductor device manufacturing sheet 101 to the jig. Further, since it is not necessary to provide a jig adhesive layer, the semiconductor device-manufacturing sheet 101 can be manufactured efficiently at low cost.

As described above, the semiconductor device manufacturing sheet 101 has an advantageous effect by not having a jig adhesive layer, but may have a jig adhesive layer. In this case, the adhesive layer for a jig is provided in a region near the peripheral edge portion of the surface of any of the layers constituting the semiconductor device manufacturing sheet 101. Such a region includes the non-laminated region on the first surface 12a of the adhesive layer 12.

The pressure-sensitive adhesive layer for a jig may be a known pressure-sensitive adhesive layer for a jig, and may have, for example, a single-layer structure containing a pressure-sensitive adhesive component, or a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.

When the semiconductor device-manufacturing sheet 101 is stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the adhesive layer 12) in a manner to be described later, that is, when so-called spreading is performed, the semiconductor device-manufacturing sheet 101 can be easily spread because the non-laminated region exists on the first surface 12a of the adhesive layer 12. Further, the film-like adhesive 14 can be easily cut, and the intermediate layer 13 and the film-like adhesive 14 can be prevented from being peeled off from the adhesive layer 12 in some cases.

In the semiconductor device-manufacturing sheet 101, the intermediate layer 13 contains a non-silicon resin having a weight-average molecular weight of 100000 or less as a main component.

The semiconductor device manufacturing sheet according to the present embodiment is not limited to the semiconductor device manufacturing sheet shown in fig. 1 and 2, and the configuration of the part of the semiconductor device manufacturing sheet shown in fig. 1 and 2 may be changed, deleted, or added within a range not to impair the effect of the present invention.

For example, the semiconductor device-manufacturing sheet of the present embodiment may include another layer not belonging to any of the substrate, the adhesive layer, the intermediate layer, the film-like adhesive, the release film, and the jig adhesive layer. However, as shown in fig. 1, the semiconductor device manufacturing sheet of the present embodiment preferably includes an adhesive layer in a state where the adhesive layer is in direct contact with a substrate, an intermediate layer in a state where the intermediate layer is in direct contact with the adhesive layer, and a film-like adhesive in a state where the film-like adhesive is in direct contact with the intermediate layer.

For example, in the semiconductor device manufacturing sheet of the present embodiment, the planar shapes of the intermediate layer and the film-like adhesive may be shapes other than circular, and the planar shapes of the intermediate layer and the film-like adhesive may be the same as or different from each other. Further, it is preferable that the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both smaller than the area of the surface of the layer closer to the substrate than the first surface of the intermediate layer (for example, the first surface of the adhesive layer), and the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive may be the same as or different from each other. The outer circumferential positions of the intermediate layer and the film-like adhesive may be uniform or non-uniform in the radial direction of these layers.

Next, the layers constituting the semiconductor device manufacturing sheet of the present embodiment will be described in more detail.

O base material

The substrate is in the shape of a sheet or a film.

The constituent material of the base material is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), and the like), polypropylene (PP), polybutene, polybutadiene, polymethylpentene, styrene-ethylenebutylene-styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, urethane acrylate, Polyimide (PI), ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ethylene copolymer other than ethylene- (meth) acrylic acid copolymer and ethylene- (meth) acrylate copolymer, polystyrene, polycarbonate, polyethylene terephthalate, and the like, Fluorine resins, hydrogenated products, modified products, crosslinked products, or copolymers of any of the above resins, and the like.

In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Similar terms to (meth) acrylic acid are also the same, for example, "(meth) acrylate" is a concept including "acrylate" and "methacrylate", and "(meth) acryl" is a concept including "acryl" and "methacryl".

The resin constituting the base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

The substrate may be composed of one layer (single layer) or a plurality of layers of two or more layers. When the substrate is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.

In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all layers may be the same or different from each other, or only a part of layers may be the same" and "a plurality of layers are different from each other" means "at least one of the constituent materials and the thicknesses of the respective layers are different from each other", not limited to the substrate.

The thickness of the base material can be suitably selected according to the purpose, and is preferably 50 to 300 μm, more preferably 60 to 150 μm. By making the thickness of the base material more than the lower limit value, the structure of the base material is more stable. By setting the thickness of the base material to the upper limit or less, the film-like adhesive can be cut more easily when the dicing is performed and when the sheet for manufacturing a semiconductor device is spread.

Here, the "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.

In order to improve the adhesion between the substrate and another layer such as an adhesive layer provided thereon, the surface of the substrate may be subjected to an embossing treatment such as a sandblasting treatment, a solvent treatment, or an embossing 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 may also be primed (primer treatment).

The substrate may also have: an antistatic coating; a layer for preventing the adhesion of the base material to other sheets or the adhesion of the base material to a suction table (suction table) when the wafers are stacked and fixed and stored.

The base material may contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin.

The optical properties of the base material are not particularly limited as long as the effects of the present invention are not impaired. The substrate may be, for example, a substrate that transmits laser light or energy rays.

The substrate can be manufactured by a known method. For example, a resin-containing (resin-constituting) substrate can be produced by molding the resin or a resin composition containing the resin.

Adhesive layer

The adhesive layer is in a sheet or film shape and contains an adhesive.

The adhesive layer can be formed using an adhesive composition containing the adhesive. For example, an adhesive composition is applied to a surface to be provided with an adhesive layer, and the applied surface is dried as needed, whereby the adhesive layer can be formed at a target site.

In the adhesive agent layer, the total content of one or two or more of the components contained in the adhesive agent layer, which will be described later, is not more than 100% by mass relative to the total mass of the adhesive agent layer.

Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the components contained in the adhesive composition, which will be described later, to the total mass of the adhesive composition is not more than 100% by mass.

The adhesive composition may be applied by a known method, and examples thereof include a method using various coating machines such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferably dried by heating, and in this case, for example, it is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes.

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferred.

In the present specification, the term "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness due to the presence of an inducer (trigger) such as heat or water, or the like.

The adhesive layer may be either curable or non-curable, and may be either energy ray-curable or non-energy ray-curable, for example. The curable adhesive layer can be easily adjusted in physical properties before and after curing.

In the present specification, "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of the energy ray include ultraviolet rays, radiation, and electron beams. For example, the ultraviolet rays may be irradiated by using a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.

In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.

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

The thickness of the adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer.

The adhesive layer is not particularly limited as long as the optical characteristics thereof are within a range that does not impair the effects of the present invention. For example, the adhesive layer may be an adhesive layer that transmits energy rays.

Next, the adhesive composition will be described.

< adhesive composition > <

When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive, that is, an energy ray-curable adhesive composition, include: an adhesive composition (I-1) comprising an adhesive resin (I-1a) which is not curable by energy rays (hereinafter, sometimes abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain of a non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)"); and an adhesive composition (I-3) comprising the adhesive resin (I-2a) and an energy ray-curable compound.

< adhesive composition (I-1) >

As described above, the adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable compound.

[ adhesive resin (I-1a) ]

Preferably, the adhesive resin (I-1a) is an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.

The acrylic resin may have only one kind of structural unit, or two or more kinds of structural units, and in the case of two or more kinds of structural units, the combination and ratio thereof may be arbitrarily selected.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ energy ray-curable Compound ]

Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include a monomer or oligomer having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.

Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.

Examples of the oligomer in the energy ray-curable compound include oligomers obtained by polymerizing the monomers exemplified above.

The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer because of its large molecular weight and the low tendency to decrease the storage modulus of the adhesive layer.

The energy ray-curable compound contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

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

[ crosslinking agent ]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.

The crosslinking agent crosslinks the adhesive resins (I-1a) to each other, for example, by reacting with the functional groups.

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa [1- (2-methyl) -azidinyl ] triphosphazine (hexa [1- (2-methyl) -azidinyl ] triphosphatriazine); metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.

The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of improving the cohesive force of the adhesive agent to improve the adhesive force of the adhesive agent layer, and in terms of easy availability.

The crosslinking agent contained in the adhesive composition (I-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1 a).

[ photopolymerization initiator ]

The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation such as ultraviolet rays.

Examples of the 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 compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as butanedione; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.

Further, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

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

[ other additives ]

The adhesive composition (I-1) may contain other additives not belonging to any of the above components within the range not impairing the effects of the present invention.

Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).

The reaction retarder is a component for suppressing the unintended crosslinking reaction in the adhesive composition (I-1) during storage, for example, due to the action of a catalyst mixed in the adhesive composition (I-1). Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by a chelate compound corresponding to a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.

The adhesive composition (I-1) may contain only one other additive, or may contain two or more other additives, and when two or more other additives are contained, the combination and ratio of these additives may be arbitrarily selected.

The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the kind thereof.

[ solvent ]

The adhesive composition (I-1) may contain a solvent. By containing the solvent, the applicability of the adhesive composition (I-1) to the surface to be coated is improved.

The solvent is preferably an organic solvent.

< adhesive composition (I-2) >

As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1 a).

[ adhesive resin (I-2a) ]

The adhesive resin (I-2a) can be 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-1 a).

The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a), in addition to the energy ray-polymerizable unsaturated group.

Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.

Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxyl group or an epoxy group.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ crosslinking agent ]

For example, when the same acrylic polymer having a 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.

The crosslinking agent in the adhesive composition (I-2) may be the same crosslinking agent as that in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-2) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).

[ photopolymerization initiator ]

The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) may be the same photopolymerization initiator as that in the adhesive composition (I-1).

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

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

[ other additives and solvents ]

The adhesive composition (I-2) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.

Further, the adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

Examples of the other additive and the solvent in the adhesive composition (I-2) include other additives and solvents similar to those in the adhesive composition (I-1).

The other additives and solvents contained in the adhesive composition (I-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.

The content of each of the other additives and the solvent in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected depending on the kind thereof.

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

[ energy ray-curable Compound ]

Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray, and examples include the same energy ray-curable compounds as those contained in the adhesive composition (I-1).

The energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

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

[ photopolymerization initiator ]

The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with a relatively low energy ray such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) may be the same photopolymerization initiator as that in the adhesive composition (I-1).

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.

[ other additives and solvents ]

The adhesive composition (I-3) may contain other additives not belonging to any of the above components within the range not impairing the effects of the present invention.

Further, the adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

Examples of the other additive and the solvent in the adhesive composition (I-3) include other additives and solvents similar to those in the adhesive composition (I-1).

The adhesive composition (I-3) may contain only one type of other additive and solvent, or two or more types of other additives and solvents, and when two or more types are contained, the combination and ratio of these may be arbitrarily selected.

The content of each of the other additives and the solvent in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected depending on the kind thereof.

< adhesive compositions other than the adhesive compositions (I-1) to (I-3) >

Although the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly described so far, the components described as the components contained therein can be similarly used in all adhesive compositions other than the three adhesive compositions (in the present specification, referred to as "adhesive compositions other than the adhesive compositions (I-1) to (I-3)").

Examples of the adhesive compositions other than the adhesive compositions (I-1) to (I-3) include energy ray-curable adhesive compositions and non-energy ray-curable adhesive compositions.

Examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, or an ester resin, and a non-energy ray-curable adhesive composition containing an acrylic resin is preferable.

The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents, and the content thereof may be set to the same level as that of the adhesive composition (I-1) or the like.

< adhesive composition (I-4) >

A preferable adhesive composition (I-4) includes, for example, an adhesive composition containing the adhesive resin (I-1a) and a crosslinking agent.

[ adhesive resin (I-1a) ]

The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same adhesive resin as the adhesive resin (I-1a) in the adhesive composition (I-1).

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ crosslinking agent ]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) may be the same crosslinking agent as that in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-4) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

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

[ other additives and solvents ]

The adhesive composition (I-4) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.

Further, the adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

Examples of the other additives and solvents in the adhesive composition (I-4) include the same additives and solvents as those in the adhesive composition (I-1).

The adhesive composition (I-4) may contain only one type of other additive and solvent, or two or more types of other additives and solvents, and when two or more types are contained, the combination and ratio of these additives and solvents can be arbitrarily selected.

The contents of other additives and solvents in the adhesive composition (I-4) are not particularly limited, and may be appropriately selected depending on the type thereof.

< method for producing adhesive composition >)

The adhesive compositions other than the adhesive compositions (I-1) to (I-3), such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4), can be obtained by blending the adhesive with components other than the adhesive, if necessary, for each component constituting the adhesive composition.

The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.

When a solvent is used, the solvent may be mixed with any of the components other than the solvent to dilute the components in advance, or the solvent may be mixed with the components without diluting any of the components other than the solvent to use.

When blending, the method of mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.

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

Intermediate layer and intermediate layer-forming composition

The intermediate layer is in the form of a sheet or a film and contains the non-silicon resin as a main component.

The intermediate layer may be a layer containing only the non-silicon resin (a layer formed of the non-silicon resin), or may be a layer containing the non-silicon resin and a component other than the non-silicon resin.

The intermediate layer can be formed using, for example, an intermediate layer-forming composition containing the non-silicone resin. For example, the intermediate layer can be formed on a target site by applying the intermediate layer-forming composition to a target surface on which the intermediate layer is to be formed and drying the composition as necessary.

In the intermediate layer, the ratio of the total content of one or two or more of the components to be described later in the intermediate layer to the total mass of the intermediate layer is not more than 100 mass%.

Similarly, in the intermediate layer-forming composition, the total content of one or two or more components contained later in the intermediate layer-forming composition does not exceed 100% by mass relative to the total mass of the intermediate layer-forming composition.

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

The drying conditions of the intermediate layer-forming composition are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferably dried by heating, and in this case, for example, it is preferably dried at 60 to 130 ℃ for 1 to 6 minutes.

The weight average molecular weight of the non-silicone resin is 100000 or less.

The weight average molecular weight of the non-silicone resin may be, for example, 80000 or less, 60000 or less, or 40000 or less, in order to further improve the suitability for dividing the semiconductor wafer of the semiconductor device manufacturing sheet.

The lower limit of the weight average molecular weight of the non-silicone resin is not particularly limited, and the non-silicone resin having a weight average molecular weight of 5000 or more, for example, is more easily obtained.

The weight average molecular weight of the non-silicone resin may be appropriately adjusted within a range set by arbitrarily combining the above lower limit value and upper limit value. For example, in one embodiment, the weight average molecular weight can be, for example, any range of 5000 to 100000, 5000 to 80000, 5000 to 60000, and 5000 to 40000.

In the present embodiment, the phrase "the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component" means "the non-silicon resin is contained in an amount sufficient to exert the effect of the intermediate layer containing the non-silicon resin having a weight average molecular weight of 100000 or less". From the above-described viewpoint, the ratio of the content of the non-silicone resin in the intermediate layer to the total mass of the intermediate layer (in other words, the ratio of the content of the non-silicone resin to the total content of all the components excluding the solvent in the intermediate layer-forming composition) is preferably 80% by mass or more, more preferably 90% by mass or more, and may be, for example, any one of the ranges of 95% by mass or more, 97% by mass or more, and 99% by mass or more.

On the other hand, the ratio is 100 mass% or less.

The non-silicon resin having a weight average molecular weight of 100000 or less is not particularly limited as long as it is a resin component having no silicon atom as a constituent atom and having a weight average molecular weight of 100000 or less.

The non-silicone 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-silicone resin is preferably a polar resin because of high solubility in the intermediate layer-forming composition and higher coatability of the intermediate layer-forming composition.

In the present specification, unless otherwise specified, "non-silicone resin" means the non-silicone resin having the above-mentioned weight-average molecular weight of 100000 or less.

The non-silicone resin may be, for example, a homopolymer of a polymer of 1 kind of monomer (in other words, having only 1 kind of structural unit), or a copolymer of a polymer of 2 or more kinds of monomers (in other words, having 2 or more kinds of structural units).

Examples of the polar group include a carbonyloxy group (-C (═ O) -O-), an oxycarbonyl group (-O-C (═ O) -), and the like.

The polar resin may have only a structural unit having a polar group, or may have both a structural unit having a polar group and a structural unit having no polar group.

As the structural unit having the polar group, for example, a structural unit derived from vinyl acetate and the like can be cited.

As the structural unit not having the polar group, for example, a structural unit derived from ethylene and the like can be cited.

In the polar resin, the proportion of the mass of the structural unit having a polar group to the total mass of all the structural units is preferably 5 to 70 mass%, and may be, for example, any one of 7.5 to 55 mass% and 10 to 40 mass%. In other words, in the polar resin, the ratio of the mass of the structural unit having no polar group to the total mass of all the structural units is preferably 30 to 95 mass%, and may be, for example, 45 to 92.5 mass% or 60 to 90 mass%. By making the ratio of the mass of the structural unit having a polar group equal to or greater than the lower limit value, the polar resin more remarkably has such a characteristic as to have a polar group. By setting the proportion of the mass of the structural unit having a polar group to the upper limit value or less, the polar resin more appropriately has such a characteristic that it does not have a polar group.

Examples of the polar resin include an ethylene-vinyl acetate copolymer.

Among these, preferable examples of the polar resin include a polar resin in which the ratio of the mass of a structural unit derived from vinyl acetate to the total mass of all structural units in an ethylene-vinyl acetate copolymer (in the present specification, it may be referred to as "the content of a structural unit derived from vinyl acetate") is 10 to 40% by mass. In other words, a preferred example of the polar resin is a polar resin in which the ratio of the mass of the structural unit derived from ethylene to the total mass of all the structural units in the ethylene-vinyl acetate copolymer is 60 to 90% by mass.

Examples of the nonpolar resin include Polyethylene (PE) such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), metallocene catalyst linear low density polyethylene (metallocene LLDPE), Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE); polypropylene (PP), and the like.

The composition for forming an intermediate layer and the non-silicone resin contained in the intermediate layer may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

For example, the composition for forming an intermediate layer and the intermediate layer may contain 1 or 2 or more kinds of non-silicone resins as polar resins and not contain non-silicone resins as non-polar resins, may contain 1 or 2 or more kinds of non-silicone resins as non-polar resins and not contain non-silicone resins as polar resins, and may contain 1 or 2 or more kinds of non-silicone resins as polar resins and 1 or 2 or more kinds of non-silicone resins as non-polar resins at the same time.

The composition for forming an intermediate layer and the intermediate layer preferably contain at least a non-silicone resin as a polar resin.

In the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin as a polar resin to the total content of the non-silicone resins is preferably 80% by mass or more, more preferably 90% by mass or more, and may be, for example, any one of the ranges of 95% by mass or more, 97% by mass or more, and 99% by mass or more. By setting the ratio to be not less than the lower limit, the effect of using the polar resin can be more remarkably obtained.

On the other hand, the ratio is 100 mass% or less.

That is, in the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin as a non-polar resin to the total content of the non-silicone resin is preferably 20% by mass or less, more preferably 10% by mass or less, and may be, for example, any one of 5% by mass or less, 3% by mass or less, and 1% by mass or less.

On the other hand, the ratio is 0 mass% or more.

From the viewpoint of good workability of the composition for forming the intermediate layer, the composition for forming the intermediate layer preferably contains a solvent in addition to the non-silicone resin, and may contain a component (in the present specification, sometimes referred to as "additive") which does not belong to any of the components of the non-silicone resin and the solvent.

The intermediate layer may contain only the non-silicone resin or may contain both the non-silicone resin and the additive.

The additive may be any one of a resin component (in this specification, sometimes referred to as "other resin component") and a non-resin component.

Examples of the other resin component include a non-silicone resin and a silicone resin having a weight average molecular weight (Mw) of more than 100000(Mw > 100000).

The non-silicone resin having a weight average molecular weight of more than 100000 is not particularly limited as long as such a condition is satisfied.

As described below, the intermediate layer containing the silicone resin facilitates the pickup of the semiconductor chip with the film-like adhesive.

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

Examples of the preferred silicone resin include a resin component that exhibits a mold release action with respect to the adhesive component, and more preferably a silicone resin (also referred to as a resin component having a siloxane bond (-Si-O-Si-) or a silicone compound).

Examples of the siloxane-based resin include polydialkylsiloxane.

The number of carbon atoms of an alkyl group of the polydialkylsiloxane is preferably 1 to 20.

In the polydialkylsiloxane, the two alkyl groups bonded to 1 silicon atom may be the same as each other or different from each other. When two alkyl groups bonded to 1 silicon atom are different from each other, the combination of the two alkyl groups is not particularly limited.

Examples of the polydialkylsiloxane include polydimethylsiloxane.

The 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 an intermediate layer and the additive contained in the intermediate layer may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio of these may be arbitrarily selected.

For example, the composition for forming an intermediate layer and the intermediate layer may contain 1 or 2 or more resin components as the additive and not contain a non-resin component, may contain 1 or 2 or more non-resin components as the additive and not contain a resin component, and may contain 1 or 2 or more resin components and 1 or 2 or more non-resin components as the additive.

When the intermediate layer-forming composition and the intermediate layer contain the additive, the ratio of the content of the non-silicone resin in the intermediate layer to the total mass of the intermediate layer (in other words, the ratio of the content of the non-silicone resin in the intermediate layer-forming composition to the total content of all components excluding the solvent) is preferably 90 to 99.99 mass%, and may be, for example, any one of 90 to 97.5 mass%, 90 to 95 mass%, and 90 to 92.5 mass%, or any one of 92.5 to 99.99 mass%, 95 to 99.99 mass%, and 97.5 to 99.99 mass%, or may be 92.5 to 97.5 mass%.

When the intermediate layer-forming composition and the intermediate layer contain the additive, the ratio of the content of the additive to the total mass of the intermediate layer in the intermediate layer (in other words, the ratio of the content of the additive to the total content of all components except the solvent in the intermediate layer-forming composition) is preferably 0.01 to 10% by mass, and for example, may be any one of 2.5 to 10% by mass, 5 to 10% by mass, and 7.5 to 10% by mass, may be any one of 0.01 to 7.5% by mass, 0.01 to 5% by mass, and 0.01 to 2.5% by mass, and may be 2.5 to 7.5% by mass.

The solvent contained in the intermediate layer-forming composition is not particularly limited, but preferable solvents include, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The intermediate layer-forming composition may contain only one kind of solvent, or two or more kinds of solvents, and in the case of two or more kinds of solvents, the combination and ratio thereof may be arbitrarily selected.

The solvent contained in the intermediate layer-forming composition is preferably tetrahydrofuran or the like, because the components contained in the intermediate layer-forming composition can be mixed more uniformly.

The content of the solvent in the intermediate layer-forming composition is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent, for example.

As described below, the preferable intermediate layer is, for example, one that can easily pick up a semiconductor chip with a film-like adhesive, as follows: and an intermediate layer containing an ethylene vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, wherein the ratio of the content of the ethylene vinyl acetate copolymer (the non-silicone resin) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical ranges described above, and the ratio of the content of the siloxane compound (the additive) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical ranges described above.

Examples of such an intermediate layer include the following intermediate layers: and an intermediate layer containing an ethylene vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, wherein the ratio of the content of the ethylene vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%. However, this is only one preferred example of an intermediate layer.

More preferable examples of the intermediate layer include the following intermediate layers: the intermediate layer contains an ethylene vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and in the ethylene vinyl acetate copolymer, the proportion of the mass of structural units derived from vinyl acetate to the total mass of all structural units (in other words, the content of structural units derived from vinyl acetate) is 10 to 40 mass%, and in the intermediate layer, the proportion of the content of the ethylene vinyl acetate copolymer to the total mass of the intermediate layer is 90 to 99.99 mass%, and in the intermediate layer, the proportion of the content of the siloxane compound to the total mass of the intermediate layer is 0.01 to 10 mass%. However, this is just one more preferable example of the intermediate layer.

When the surface of the film-like binder side of the intermediate layer (for example, the first surface 13a of the intermediate layer 13 in fig. 1) is analyzed by X-ray Photoelectron Spectroscopy (in this specification, it may be referred to as "XPS"), the ratio of the concentration of silicon (in this specification, it may be referred to simply as "the ratio of the silicon concentration") to the total concentration of carbon, oxygen, nitrogen and silicon is preferably 1 to 20% on an elemental molar basis. As described below, by using the semiconductor device manufacturing sheet provided with such an intermediate layer, it is possible to easily pick up a semiconductor chip with a film-like adhesive.

For XPS analysis, an X-ray photoelectron spectroscopy apparatus can be used, and the X-ray irradiation angle is 45 DEG and the X-ray beam diameter is 45 DEG

The surface of the intermediate layer to be analyzed on the film-like adhesive side was subjected to XPS analysis under the condition that the output was 4.5W.

The ratio of the silicon concentration can be calculated by the following formula.

[ measured value of silicon concentration (atomic%) based on XPS analysis ]/{ [ measured value of carbon concentration (atomic%) based on XPS analysis ] + [ measured value of oxygen concentration (atomic%) based on XPS analysis ] + [ measured value of nitrogen concentration (atomic%) based on XPS analysis ] + [ measured value of silicon concentration (atomic%) based on XPS analysis ] } 100 ×

From the viewpoint of further enhancing the above-mentioned effect, the proportion of the silicon concentration may be, for example, any one of 4 to 20%, 8 to 20% and 12 to 20%, 1 to 16%, 1 to 12% and 1 to 8%, and 4 to 16% and 8 to 12% on a molar basis of the element.

When the XPS analysis is performed as described above, there is a possibility that another element not belonging to any of carbon, oxygen, nitrogen, and silicon may be detected on the surface of the intermediate layer (the surface to be analyzed by XPS). However, since the concentration of the other elements is usually minute even when the other elements are detected, the ratio of the silicon concentration can be calculated with high accuracy by using the measured values of the concentrations of carbon, oxygen, nitrogen, and silicon when the ratio of the silicon concentration is calculated.

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

As described 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 base material.

The maximum value of the width of the intermediate layer may be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the intermediate layer may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. These 3 numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to a surface to be bonded to the semiconductor device manufacturing sheet of 150mm, 200mm, or 300 mm. However, as described above, when the film-like adhesive is cut by expanding the semiconductor device manufacturing sheet after dicing accompanied by formation of the modified layer in the semiconductor wafer, a plurality of semiconductor chips (semiconductor chip groups) after dicing are collectively joined together, and the semiconductor device manufacturing sheet is attached to these semiconductor chips, as described below.

In the present 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 face of the intermediate layer". For example, in the case of an intermediate layer having a circular planar shape, the maximum value of the width of the intermediate layer is the diameter of a circle having the planar shape.

This is also the case for semiconductor wafers. That is, the "width of the semiconductor wafer" means,

"width of the semiconductor wafer in a direction parallel to a surface of the semiconductor wafer to be bonded to the semiconductor device manufacturing sheet". For example, in the case of a semiconductor wafer having a circular planar shape, the maximum value of the width of the semiconductor wafer is the diameter of a circle having the planar shape.

The maximum value of the width of the intermediate layer of 150 to 160mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 150mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the intermediate layer of 200 to 210mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 200mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the intermediate layer of 300 to 310mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 300mm in a range of not more than 10 mm.

That is, in the present embodiment, the difference between the maximum value of the width of the intermediate layer and the maximum value of the width of the semiconductor wafer may be, for example, 0 to 10mm, regardless of which value of 150mm, 200mm and 300mm the maximum value of the width of the semiconductor wafer is.

The thickness of the intermediate layer is suitably selected according to the purpose, preferably 5 to 150 μm, more preferably 5 to 120 μm, and for example, may be in any range of 10 to 90 μm and 10 to 60 μm, and may be in any range of 30 to 120 μm and 60 to 120 μm. By making the thickness of the intermediate layer more than the lower limit value, the structure of the intermediate layer is more stable. By setting the thickness of the intermediate layer to the upper limit or less, the film-like adhesive can be cut more easily when the dicing is performed and when the expansion of the sheet for manufacturing a semiconductor device is performed.

Here, the "thickness of the intermediate layer" refers to the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers refers to the total thickness of all layers constituting the intermediate layer.

When the intermediate layer contains the silicone-based resin, particularly when the compatibility of the silicone-based resin with the non-silicone-based resin as a main component is low, the silicone-based resin in the intermediate layer tends to unevenly exist on both surfaces (the first surface and the surface opposite to the first surface) of the intermediate layer and in the vicinity thereof in the sheet for manufacturing a semiconductor device. Further, the stronger this tendency, the more easily the film-like adhesive adjacent to the intermediate layer (directly contacting the intermediate layer) is peeled off from the intermediate layer, and the more easily the semiconductor chip with the film-like adhesive can be picked up as described below.

For example, when intermediate layers having different thicknesses but the same composition, area of both surfaces, and the like except for the thickness are compared with each other, the proportions (mass%) of the content of the silicone-based resin with respect to the total mass of the intermediate layers are the same among the intermediate layers. However, the amount (parts by mass) of the silicone resin in the intermediate layer is larger in the intermediate layer having a larger thickness than in the intermediate layer having a smaller thickness. Therefore, when the silicon-based resin is likely to be unevenly present in the intermediate layer as described above, the amount of the silicon-based resin unevenly present on both surfaces (the first surface and the surface opposite to the first surface) and the vicinity thereof of the intermediate layer having a larger thickness is larger than that of the intermediate layer having a smaller thickness. Therefore, the pick-up suitability of the semiconductor chip with the film-like adhesive can be adjusted by adjusting the thickness of the intermediate layer in the semiconductor device-manufacturing sheet without changing the ratio. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, it is possible to more easily pick up the semiconductor chip with the film-like adhesive.

Film-like adhesive

The film-like adhesive has curability, preferably thermosetting, and preferably pressure-sensitive adhesiveness. A film-like adhesive having both thermosetting and pressure-sensitive adhesiveness can be attached to various adherends by lightly pressing in an uncured state. The film-like adhesive may be an adhesive capable of being attached to various adherends by softening the adhesive by heating. The film-like adhesive is cured to finally form a cured product having high impact resistance, and the cured product can maintain sufficient adhesive properties even under severe conditions of high temperature and high humidity.

When the semiconductor device manufacturing sheet is viewed from above in a downward direction, the area of the film-like adhesive (i.e., the area of the first surface) is preferably set to be smaller than the area of the base material (i.e., the area of the first surface) and the area of the adhesive layer (i.e., the area of the first surface) so as to be close to the area of the semiconductor wafer before dicing. In such a semiconductor device manufacturing sheet, a region not in contact with the intermediate layer and the film-like adhesive (i.e., the non-lamination region) is present in a part of the first surface of the adhesive layer. This makes it easier to expand the sheet for manufacturing a semiconductor device, and also makes it easier to cut the film-like adhesive because the force applied to the film-like adhesive during expansion is not dispersed.

The film-like adhesive can be formed using an adhesive composition containing the constituent materials thereof. For example, a film-shaped adhesive can be formed on a target site by applying an adhesive composition to a target surface on which a film-shaped adhesive is to be formed and drying the adhesive composition as needed.

In the film-shaped adhesive, the total content of one or two or more components to be described later in the film-shaped adhesive is not more than 100% by mass relative to the total mass of the film-shaped adhesive.

Similarly, in the binder composition, the total content of one or two or more components contained in the binder composition, which will be described later, is not more than 100% by mass relative to the total mass of the binder composition.

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

The drying conditions of the adhesive composition are not particularly limited. When the binder composition contains a solvent described later, it is preferably dried by heating, and in this case, for example, it is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes.

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

As described above, the maximum value of the width of the film-like 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 value of the width of the film-like adhesive may be the same as the maximum value of the width of the intermediate layer explained above with respect to the size of the semiconductor wafer.

That is, the maximum value of the width of the film-like adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the film-like adhesive may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. These three numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to a surface to which the semiconductor device manufacturing sheet is attached of 150mm, 200mm, or 300 mm.

In the present specification, unless otherwise specified, "the width of the film-like adhesive" refers to, for example, "the width of the film-like adhesive in a direction parallel to the first face of the film-like adhesive". For example, in the case of a film-shaped adhesive having a circular planar shape, the maximum value of the width of the film-shaped adhesive is the diameter of the circle having 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 (not cutting)" and is not the width of the film-like adhesive after cutting in the manufacturing process of the semiconductor chip with the film-like adhesive described later.

The maximum value of the width of the film-like adhesive of 150 to 160mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 150mm within a range of not more than 10 mm.

Similarly, the maximum value of the width of the film-like adhesive of 200 to 210mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 200mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the film-like adhesive of 300 to 310mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 300mm in a range of not more than 10 mm.

That is, in the present embodiment, the difference between the maximum value of the width of the film-like adhesive and the maximum value of the width of the semiconductor wafer may be, for example, 0 to 10mm, regardless of which value of 150mm, 200mm and 300mm the maximum value of the width of the semiconductor wafer is.

In the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film-shaped adhesive may be any one of the above numerical value ranges.

That is, as an example of the sheet for manufacturing a semiconductor device of the present embodiment, there can be mentioned a sheet for manufacturing a semiconductor device in which the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive are 150 to 160mm, 200 to 210mm, or 300 to 310 mm.

The thickness of the film-like adhesive is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm, and particularly preferably 3 to 10 μm. By setting the thickness of the film-like pressure-sensitive adhesive to the lower limit or more, a higher adhesive force to an adherend (semiconductor chip) can be obtained. By setting the thickness of the film-like adhesive to the upper limit or less, the film-like adhesive can be cut more easily when the dicing is performed and when the expansion of the sheet for manufacturing a semiconductor device is performed.

The "thickness of the film-like adhesive" refers to the thickness of the entire film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers refers to the total thickness of all the layers constituting the film-like adhesive.

Next, the adhesive composition will be described.

< adhesive composition > <

A preferable adhesive composition includes, for example, an adhesive composition containing a polymer component (a) and a thermosetting component (b). Hereinafter, each component will be described.

The adhesive compositions shown below are merely preferred examples, and the adhesive composition of the present embodiment is not limited to the adhesive compositions shown below.

[ Polymer component (a) ]

The polymer component (a) is a component formed by polymerization of a polymerizable compound, and is a polymer compound that imparts film formability, flexibility, and the like to a film-like adhesive and improves adhesiveness (in other words, adhesiveness) to an object to be adhered such as a semiconductor chip. The polymer component (a) has thermoplasticity, but does not have thermosetting property. In this specification, the polymer compound also includes a product of polycondensation reaction.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.

Among them, the polymer component (a) is preferably an acrylic resin.

In the adhesive composition, the proportion of the content of the polymer component (a) to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) in the film-shaped adhesive to the total mass of the film-shaped adhesive) is preferably 20 to 75 mass%, more preferably 30 to 65 mass%.

[ thermosetting component (b) ]

The thermosetting component (b) is a component having thermosetting properties for thermosetting the film-like adhesive.

The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

Examples of the thermosetting component (b) include epoxy thermosetting resins, polyimide resins, and unsaturated polyester resins.

Among them, the thermosetting component (b) is preferably an epoxy thermosetting resin.

O epoxy thermosetting resin

The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b 2).

The epoxy thermosetting resin contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio of these may be arbitrarily selected.

Epoxy resin (b1)

Examples of the epoxy resin (b1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac (novolak) epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The compatibility of the epoxy resin having an unsaturated hydrocarbon group with the acrylic resin is greater than the compatibility of the epoxy resin having no unsaturated hydrocarbon group with the acrylic resin. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained using the film-like adhesive is increased.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

Heat-curing agent (b2)

The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b 1).

Examples of the thermosetting agent (b2) include compounds having two or more functional groups reactive with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and preferably a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group, and the like, and more preferably a phenolic hydroxyl group or an amino group.

Examples of the phenol curing agent having a phenolic hydroxyl group in the heat curing agent (b2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.

Examples of the amine-based curing agent having an amino group in the thermosetting agent (b2) include Dicyandiamide (DICY).

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

The heat-curing agent (b2) contained in the adhesive composition and the film-like adhesive may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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 to 200 parts by mass, and may be, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (b 1). When the content of the thermosetting agent (b2) is not less than the lower limit value, the film-like adhesive can be more easily cured. When the content of the thermosetting agent (b2) is not more than the upper limit, the moisture absorption rate of the film-like adhesive decreases, and the reliability of the package obtained by using the film-like adhesive further increases.

In the adhesive composition and the film-like adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b 2)) is preferably 5 to 100 parts by mass, more preferably 5 to 75 parts by mass, particularly preferably 5 to 50 parts by mass, and may be, for example, 5 to 35 parts by mass or 5 to 20 parts by mass, based on 100 parts by mass of the content of the polymer component (a). By making the content of the thermosetting component (b) within the above range, the peeling force between the intermediate layer and the film-like adhesive is more stabilized.

In order to improve various physical properties of the film-shaped adhesive, the adhesive composition and the film-shaped adhesive may further contain other components not belonging to the polymer component (a) and the thermosetting component (b) as necessary, in addition to the polymer component (a) and the thermosetting component (b).

Preferable examples of the other components contained in the adhesive composition and the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), a photopolymerization initiator (h), and a general-purpose additive (i).

[ curing Accelerator (c) ]

The curing accelerator (c) is a component for adjusting the curing speed of the adhesive composition.

Examples of the preferable curing accelerator (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom), such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium (tetraphenylphosphonium borate) and triphenylphosphine tetraphenylboron (triphenylphosphonium tetraphenylboronate).

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the curing accelerator (c) is used, the content of the curing accelerator (c) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the thermosetting component (b) in the adhesive composition and the film-like adhesive. By setting the content of the curing accelerator (c) to the lower limit or more, the effect of using the curing accelerator (c) can be more remarkably obtained. When the content of the curing accelerator (c) is not more than the above upper limit, for example, the effect of suppressing the migration of the highly polar curing accelerator (c) to the side of the adhesive interface with the adherend in the film-like adhesive under high temperature and high humidity conditions and the occurrence of segregation increases, and the reliability of the package obtained using the film-like adhesive further increases.

[ Filler (d) ]

By containing the filler (d) in the film-like adhesive, the cuttability by the spread film-like adhesive is further improved. Further, by containing the filler (d) in the film-like adhesive, the thermal expansion coefficient of the film-like adhesive can be easily adjusted, and by optimizing the thermal expansion coefficient with respect to the object to which the film-like adhesive is attached, the reliability of the package obtained by using the film-like adhesive is further improved. Further, by containing the filler (d) in the film-shaped adhesive, the moisture absorption rate of the cured film-shaped adhesive can be reduced or the heat dissipation property can be improved.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads (beads) obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like.

Among them, the inorganic filler is preferably silica or alumina.

The filler (d) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the filler (d) is used, the content of the filler (d) in the adhesive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass, based on the total content of all the components except the solvent (i.e., the content of the filler (d) in the film-shaped adhesive based on the total mass of the film-shaped adhesive). By setting the ratio within the above range, the effect of using the filler (d) can be more remarkably obtained.

[ coupling agent (e) ]

When the film-shaped pressure-sensitive adhesive contains the coupling agent (e), the adhesiveness and adhesiveness to an adherend are improved. Further, by containing the coupling agent (e) in the film-shaped adhesive, the water resistance of the cured product of the film-shaped adhesive is improved without impairing the heat resistance. The coupling agent (e) has a functional group reactive with an inorganic compound or an organic compound.

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

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the coupling agent (e) is used, the content of the coupling agent (e) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b) in the adhesive composition and the film-like adhesive. By setting the content of the coupling agent (e) to the lower limit or more, the effects of using the coupling agent (e), that is, improvement in dispersibility of the filler (d) in the resin, improvement in adhesiveness between the film-shaped adhesive and the adherend, and the like can be more remarkably obtained. By setting the content of the coupling agent (e) to the upper limit value or less, the generation of outgas (out-gas) can be further suppressed.

[ crosslinking agent (f) ]

When a substance having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which can be bonded to another compound, such as the acrylic resin, is used as the polymer component (a), the adhesive composition and the film-like adhesive may contain the crosslinking agent (f). The crosslinking agent (f) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the film-shaped adhesive can be adjusted.

Examples of the crosslinking agent (f) include an organic polyisocyanate (polyisocynate) compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.

When an organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl group-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinked structure can be easily introduced into the film-like adhesive by the reaction of the crosslinking agent (f) with the polymer component (a).

The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the crosslinking agent (f) to the lower limit or more, the effect of using the crosslinking agent (f) can be more remarkably obtained. By making the content of the crosslinking agent (f) the upper limit value or less, the excessive use of the crosslinking agent (f) can be suppressed.

Energy ray-curable resin (g)

When the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the film-like adhesive can be changed in properties by irradiation with an energy ray.

The energy ray-curable resin (g) is a resin obtained from an energy ray-curable compound.

Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.

The energy ray-curable resin (g) contained in the adhesive composition may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the energy ray-curable resin (g) is used, the content of the energy ray-curable resin (g) in the adhesive composition is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition.

[ photopolymerization initiator (h) ]

When the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the photopolymerization initiator (h) may be contained in order to efficiently advance the polymerization reaction of the energy ray-curable resin (g).

Examples of the photopolymerization initiator (h) in the adhesive composition 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 compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzylphenylsulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as butanedione; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

The photopolymerization initiator (h) contained in the adhesive composition may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

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

[ general additive (i) ]

The general-purpose additive (i) may be a known additive, may be arbitrarily selected according to the purpose, and is not particularly limited, but preferable additives include, for example, a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent (gettering agent), and the like.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

The content of the adhesive composition and the film-like adhesive is not particularly limited, and may be appropriately selected according to the purpose.

[ solvent ]

The adhesive composition preferably further contains a solvent. The workability of the adhesive composition containing a solvent is improved.

The solvent is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The binder composition may contain only one kind of solvent, or two or more kinds of solvents, and in the case of two or more kinds of solvents, the combination and ratio of the solvents can be arbitrarily selected.

The solvent contained in the pressure-sensitive adhesive composition is preferably methyl ethyl ketone or the like, because the components contained in the pressure-sensitive adhesive composition can be mixed more uniformly.

The content of the solvent in the adhesive composition is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.

< method for producing adhesive composition >)

The binder composition can be obtained by blending the respective components for constituting the binder composition.

For example, the adhesive composition can be prepared by the same method as the adhesive composition described above, except that the kinds of the blending components are different.

Manufacturing method of semiconductor device manufacturing wafer

The semiconductor device manufacturing sheet can be manufactured by stacking the layers so that the layers are in a corresponding positional relationship. The formation method of each layer is the same as that described above.

For example, the semiconductor device manufacturing sheet can be manufactured by: a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive are prepared in advance, and the substrate, the adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order.

However, this is just one example of a method for manufacturing a sheet for manufacturing a semiconductor device.

The semiconductor device manufacturing sheet can be manufactured, for example, by: 2 or more kinds of intermediate laminates each composed of a plurality of layers to constitute a sheet for manufacturing a semiconductor device are prepared in advance, and these intermediate laminates are bonded to each other. The structure of the intermediate laminated body can be appropriately selected arbitrarily. For example, a semiconductor device manufacturing sheet can be manufactured by previously manufacturing a first intermediate laminate (corresponding to the support sheet) having a configuration in which a base material and an adhesive layer are laminated, and a second intermediate laminate having a configuration in which an intermediate layer and a film-like adhesive are laminated, and bonding the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate.

However, this is also only an example of a method for manufacturing a sheet for manufacturing a semiconductor device.

In the case of manufacturing a semiconductor device-manufacturing sheet in which both the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are smaller than the area of the first surface of the adhesive layer and the area of the first surface of the substrate, as shown in fig. 1, for example, a step of processing the intermediate layer and the film-like adhesive into desired dimensions may be added at any stage in the above-described manufacturing method. For example, in the manufacturing method using the second intermediate laminate, the semiconductor device manufacturing sheet can be manufactured by additionally performing a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate into a target size.

When a semiconductor device-manufacturing sheet having a release film on a film-like adhesive is manufactured, for example, the film-like adhesive may be manufactured on the release film, and the remaining layers may be stacked while maintaining this state to manufacture a semiconductor device-manufacturing sheet; the sheet for manufacturing a semiconductor device may be produced by laminating all of the substrate, the adhesive layer, the intermediate layer, and the film-like adhesive, and then laminating a release film on the film-like adhesive. The release film may be removed at a necessary stage before using the sheet for manufacturing a semiconductor device.

The sheet for manufacturing a semiconductor device, which is provided with another layer that does not belong to any of the base material, the adhesive layer, the intermediate layer, the film-like adhesive, and the release film, can be manufactured by adding a step of forming and laminating the other layer at an appropriate timing in the above-described manufacturing method.

As a preferable example of the semiconductor device-manufacturing sheet of the present embodiment, there can be mentioned:

a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,

the intermediate layer contains at least a polar resin as the non-silicone resin,

in the intermediate layer, the ratio of the content of the non-silicon resin to the total mass of the intermediate layer is in any range of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the intermediate layer, the proportion of the content of the non-silicone resin that is the polar resin to the total content of the non-silicone resin is in any one range of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%.

As another preferable example of the semiconductor device-manufacturing sheet of the present embodiment, there can be mentioned:

a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,

the intermediate layer contains at least a polar resin as the non-silicone resin,

in the intermediate layer, the proportion of the content of the non-silicon resin relative to the total mass of the intermediate layer is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the intermediate layer, the proportion of the content of the non-silicone resin that is the polar resin to the total content of the non-silicone resin is in any one range of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is any one of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,

when the surface of the intermediate layer on the film-shaped adhesive side is analyzed by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon is in any one of the ranges of 1 to 20%, 4 to 16% and 8 to 12%.

As another preferable example of the semiconductor device-manufacturing sheet of the present embodiment, there can be mentioned:

a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component and further contains a silicon resin,

the intermediate layer contains at least a polar resin as the non-silicone resin,

in the intermediate layer, the content of the non-silicon resin is in any range of 90-99.99 mass%, 90-97.5 mass%, 90-95 mass% and 90-92.5 mass% relative to the total mass of the intermediate layer,

in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is in any range of 0.01 to 10 mass%, 2.5 to 10 mass%, 5 to 10 mass%, and 7.5 to 10 mass%,

wherein the ratio of the total content of the non-silicone resin and the silicone resin in the intermediate layer to the total mass of the intermediate layer is not more than 100% by mass,

in the intermediate layer, the proportion of the content of the non-silicone resin that is the polar resin to the total content of the non-silicone resin is in any one range of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%.

As another preferable example of the semiconductor device-manufacturing sheet of the present embodiment, there can be mentioned:

a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component and further contains a silicon resin,

the intermediate layer contains at least a polar resin as the non-silicone resin,

in the intermediate layer, the content of the non-silicon resin is in any range of 90-99.99 mass%, 90-97.5 mass%, 90-95 mass% and 90-92.5 mass% relative to the total mass of the intermediate layer,

in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is in any range of 0.01 to 10 mass%, 2.5 to 10 mass%, 5 to 10 mass%, and 7.5 to 10 mass%,

wherein the ratio of the total content of the non-silicone resin and the silicone resin in the intermediate layer to the total mass of the intermediate layer is not more than 100% by mass,

in the intermediate layer, the proportion of the content of the non-silicone resin that is the polar resin to the total content of the non-silicone resin is in any one range of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,

in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in any range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,

the thickness of the intermediate layer is within any range of 5-150 μm, 5-120 μm, 30-120 μm and 60-120 μm.

Method of using sheet for semiconductor device fabrication (method of fabricating semiconductor chip with film-like adhesive)

The sheet for manufacturing a semiconductor device can be used in the manufacturing process of a semiconductor device when manufacturing a semiconductor chip with a film-like adhesive.

A method of using the sheet for manufacturing a semiconductor device (a method of manufacturing a semiconductor chip with a film-like adhesive) will be described in detail below with reference to the drawings.

Fig. 3A, 3B, and 3C are cross-sectional views schematically illustrating an example of a method of using a sheet for manufacturing a semiconductor device, in which the sheet for manufacturing a semiconductor device is attached to a semiconductor wafer and then used. In this method, a semiconductor device manufacturing sheet is used as a dicing die. Here, a method of using the sheet 101 for manufacturing a semiconductor device shown in fig. 1 will be described as an example.

First, as shown in fig. 3A, while heating the semiconductor device manufacturing sheet 101 from which the release film 15 has been removed, the film-like adhesive 14 is stuck to the back surface 9b 'of the semiconductor wafer 9'.

Reference numeral 9a 'denotes a circuit forming surface of the semiconductor wafer 9'.

The heating temperature for bonding the semiconductor device manufacturing sheet 101 is not particularly limited, but is preferably 40 to 70 ℃ from the viewpoint of further improving the stability of the semiconductor device manufacturing sheet 101 in the heat bonding.

Width W of intermediate layer 13 in semiconductor device manufacturing sheet 101₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄Is equal to the width W of the semiconductor wafer 9_9’Are exactly the same or, although different, are slightly to nearly identical in error.

For example, when the width W of the semiconductor wafer 9_9’Has a maximum value of 150mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (a) is preferably 150 to 160mm when the width W of the semiconductor wafer 9_9’Has a maximum value of 200mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (a) is preferably 200 to 210mm when the width W of the semiconductor wafer 9_9’At a maximum value of 300mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (A) is preferably 300 to 310 mm.

Thus, in the present embodiment, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of the semiconductor wafer 9_9’The difference of the maximum values of (a) and the width W of the film-like adhesive 14₁₄Maximum value of (d) and width W of the semiconductor wafer 9_9’The difference of the maximum values of (A) can be 0-10 mm.

Here, the width W of the semiconductor wafer 9_9’Refers to, for example, the width of the semiconductor wafer 9 'in a direction parallel to the back surface 9 b' thereof.

Next, a blade is cut (diced) into the laminated body of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9 'obtained as described above from the circuit forming surface 9 a' side of the semiconductor wafer 9 ', thereby dividing the semiconductor wafer 9' and cutting the film-like adhesive 14.

The blade cutting can be performed by a known method. For example, the semiconductor wafer 9' can be divided and the film-like adhesive 14 can be cut by a dicing blade after fixing a region (the non-lamination region) near the peripheral edge portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101 to a jig (not shown) such as a ring frame.

As shown in fig. 3B, in this step, a plurality of semiconductor chips 914 with a film-like adhesive are obtained, each of which includes the semiconductor chip 9 and the cut film-like adhesive 140 provided on the back surface 9B thereof. These semiconductor chips 914 with a film adhesive are aligned and fixed on the intermediate layer 13 in the laminate sheet 10, and constitute a semiconductor chip group 910 with a film adhesive.

The rear side 9b of the semiconductor chip 9 corresponds to the rear side 9b 'of the semiconductor wafer 9'. In fig. 3B, reference numeral 9a denotes a circuit formation surface of the semiconductor chip 9, which corresponds to the circuit formation surface 9a 'of the semiconductor wafer 9'.

In performing blade cutting, it is preferable that: the film-like adhesive 14 is cut over the entire thickness direction thereof without cutting into the adhesive layer 12 by cutting a blade into the entire thickness direction of the semiconductor wafer 9' to divide the same and cutting the blade from the first surface 14a of the film-like adhesive 14 into an intermediate region of the intermediate layer 13 of the semiconductor device manufacturing sheet 101.

That is, when blade cutting is performed, it is preferable that: the blade is cut from the circuit-formed surface 9a ' of the semiconductor wafer 9 ' into at least the first surface 13a of the intermediate layer 13 and not into the surface of the intermediate layer 13 opposite to the first surface 13a (i.e., the surface in contact with the adhesive layer 12) in the lamination direction of the laminated body of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9 '.

In this step, the blade can be easily prevented from reaching the base material 11 by the above-described method, and thus the generation of chips from the base material 11 can be suppressed. Further, by making the main component of the intermediate layer 13 cut by the blade a non-silicone resin having a weight average molecular weight of 100000 or less, particularly by making the weight average molecular weight of 100000 or less, it is possible to suppress the generation of chips from the intermediate layer 13.

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

As shown in fig. 3C, after the blade dicing is performed, the semiconductor chip 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminated sheet 10 to be picked up. Here, a case is shown in which the semiconductor chip 914 with a film-like adhesive is pulled away in the direction of arrow P by using a pulling-away tool 7 such as a vacuum nozzle (vacuum collet). The pull-off tool 7 is not shown here in cross section.

The semiconductor chip 914 with the film-like adhesive can be picked up by a known method.

When the ratio of the silicon concentration in the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with the film adhesive can be more easily picked up.

When the intermediate layer 13 contains, for example, an ethylene vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and the ratio of the content of the ethylene vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.

Preferred embodiments of the method for manufacturing a semiconductor chip with a film-like adhesive described above include, for example:

a method for manufacturing a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip,

the sheet for manufacturing a semiconductor device comprises the substrate, an adhesive layer, an intermediate layer, and a film-like adhesive,

the manufacturing method comprises: a step of heating the semiconductor device manufacturing sheet while adhering the film-like adhesive to the back surface of the semiconductor wafer; a step of cutting the semiconductor wafer to which the film-shaped adhesive is attached into the entire region in the thickness direction thereof from the circuit forming surface side thereof to thereby produce the semiconductor chip, and cutting the semiconductor device manufacturing sheet into the middle region of the intermediate layer in the thickness direction thereof from the film-shaped adhesive side thereof, thereby obtaining a plurality of semiconductor chip groups with the film-shaped adhesive, in which the semiconductor chips with the film-shaped adhesive are aligned on the intermediate layer, by cutting the film-shaped adhesive without cutting the film-shaped adhesive into the adhesive layer; and a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, the step may be referred to as "manufacturing method 1").

Fig. 4A, 4B, and 4C are cross-sectional views schematically illustrating an example of a method for manufacturing semiconductor chips to be used as a sheet for manufacturing a semiconductor device, and show a case where semiconductor chips are manufactured by dicing accompanied by formation of a modified layer in a semiconductor wafer.

Fig. 5A, 5B, and 5C are cross-sectional views schematically illustrating another example of a method of using a sheet for manufacturing a semiconductor device, in which the sheet for manufacturing a semiconductor device is used after being attached to a semiconductor chip. In this method, the semiconductor device manufacturing sheet is used as a solid wafer. Here, a method of using the sheet 101 for manufacturing a semiconductor device shown in fig. 1 will be described as an example.

First, before using the semiconductor device manufacturing sheet 101, as shown in fig. 4A, a semiconductor wafer 9 'is prepared, and a back-grinding tape (also referred to as a surface protective tape) 8 is attached to the circuit forming surface 9 a'.

In FIG. 4A, reference numeral W_9’Indicating the width of the semiconductor wafer 9'.

Next, as shown in fig. 4B, a laser beam (not shown) is irradiated so as to be focused on a focal point set in the semiconductor wafer 9 ', thereby forming a modified layer 90 ' in the semiconductor wafer 9 '.

The semiconductor wafer 9 ' is preferably irradiated with the laser light from the back surface 9b ' side of the semiconductor wafer 9 '.

The position of the focal point at this time is a position to be divided (diced) of the semiconductor wafer 9 ', and the position is set so that a target size, shape, and number of semiconductor chips can be obtained from the semiconductor wafer 9'.

Next, the back surface 9b 'of the semiconductor wafer 9' is polished by a polishing machine (not shown). Thus, the thickness of the semiconductor wafer 9 'is adjusted to a target value, and the semiconductor wafer 9' is divided at the portion where the modified layer 90 'is formed by using the force applied to the semiconductor wafer 9' at the time of polishing, thereby producing a plurality of semiconductor chips 9 as shown in fig. 4C.

Unlike other portions of the semiconductor wafer 9 ', the modified layer 90 ' of the semiconductor wafer 9 ' is modified by irradiation with laser light, and the strength thereof becomes weak. Therefore, by applying a force to the semiconductor wafer 9 ' on which the modified layer 90 ' is formed, a force is applied to the modified layer 90 ', and the semiconductor wafer 9 ' is cracked at the modified layer 90 ', whereby a plurality of semiconductor chips 9 can be obtained.

In this way, the semiconductor chip 9 to be used as the semiconductor device manufacturing sheet 101 can be obtained. More specifically, in this step, the semiconductor chip group 901 can be obtained in which the plurality of semiconductor chips 9 are fixed to the back-grinding tape 8 in an aligned state.

When the semiconductor chip group 901 is viewed from above the semiconductor chip group 901 downward, a planar shape formed by connecting outermost portions of the semiconductor chip group 901 (in this specification, such a planar shape may be simply referred to as a "planar shape of the semiconductor chip group") is completely the same as a planar shape of the semiconductor wafer 9 ' when the semiconductor wafer 9 ' is viewed from above in the same manner, or a difference between planar shapes of the two is negligible, and the planar shape of the semiconductor chip group 901 may be said to be substantially the same as the planar shape of the semiconductor wafer 9 '.

Thus, as shown in FIG. 4C, the plane of the semiconductor chip set 901The width of the shape can be regarded as the width W of the semiconductor wafer 9_9’The same is true. The maximum value of the width of the planar shape of the semiconductor chip group 901 can be regarded as the width W of the semiconductor wafer 9_9’Are the same.

Although the semiconductor chips 9 can be formed from the semiconductor wafer 9 'as intended, a partial region of the semiconductor wafer 9' may not be divided into the semiconductor chips 9 depending on the conditions for polishing the back surface 9b 'of the semiconductor wafer 9'.

Next, using the semiconductor chip 9 (semiconductor chip group 901) obtained above, a semiconductor chip with a film-like adhesive is manufactured.

First, as shown in fig. 5A, while one piece of the semiconductor device manufacturing sheet 101 from which the release film 15 is removed is heated, the film-like adhesive 14 is attached to the back surfaces 9b of all the semiconductor chips 9 in the semiconductor chip group 901. The film-like adhesive 14 may be a semiconductor wafer that is not completely divided.

Width W of intermediate layer 13 in semiconductor device manufacturing sheet 101₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄Is equal to the width W of the semiconductor wafer 9_9’(in other words, the width of the semiconductor chip group 901) is the same or slightly different but almost equivalent.

Namely, the width W of the intermediate layer 13₁₃The relationship between the maximum value of (b) and the maximum value of the width of the semiconductor chip group 901 may be the width W of the intermediate layer 13 described previously₁₃Maximum value of (d) and width W of the semiconductor wafer 9_9’The same relationship is used between the maximum values of (a). Further, the width W of the film-like adhesive 14₁₄The relationship between the maximum value of (2) and the maximum value of the width of the semiconductor chip group 901 may be the width W of the film-like adhesive 14 described previously₁₄Maximum value of (d) and width W of the semiconductor wafer 9_9’The same relationship is used between the maximum values of (a).

The film-like adhesive 14 (semiconductor device manufacturing sheet 101) can be applied to the semiconductor chip group 901 in this case by the same method as the film-like adhesive 14 (semiconductor device manufacturing sheet 101) applied to the semiconductor wafer 9 'in the above-described manufacturing method 1, except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9'.

Next, the back-grinding tape 8 is removed from the semiconductor chip group 901 in a fixed state. Then, as shown in fig. 5B, the semiconductor device manufacturing sheet 101 is stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the adhesive layer 12) while being cooled, thereby spreading. Here, with arrow E₁The direction of expansion of the semiconductor device manufacturing sheet 101 is shown. By spreading in this manner, the film-like adhesive 14 can be cut along the outer periphery of the semiconductor chip 9.

Through this step, a plurality of semiconductor chips 914 with film-like adhesive are obtained, each of which includes the semiconductor chip 9 and the cut film-like adhesive 140 provided on the back surface 9b thereof. These semiconductor chips 914 with a film adhesive are aligned and fixed on the intermediate layer 13 in the laminate sheet 10, and constitute a semiconductor chip group 910 with a film adhesive.

The semiconductor chip 914 with a film adhesive and the semiconductor chip group 910 with a film adhesive obtained here are basically the same as the semiconductor chip 914 with a film adhesive and the semiconductor chip group 910 with a film adhesive obtained in the above-described manufacturing method 1.

When a part of the region of the semiconductor wafer 9 'is not divided into the semiconductor chips 9 when the semiconductor wafer 9' is divided as described above, the region can be divided into the semiconductor chips by performing this step.

The temperature of the semiconductor device manufacturing sheet 101 is preferably set to-5 to 5 ℃ and expanded. By cooling and expanding (cold expanding) the semiconductor device manufacturing sheet 101 in the above-described manner, the film-like adhesive 14 can be cut more easily with high accuracy.

The expansion of the semiconductor device manufacturing sheet 101 can be performed by a known method. For example, after a region (the non-lamination region) near the peripheral edge portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 in the semiconductor device-producing sheet 101 is fixed to a jig (not shown) such as a ring frame, the entire region of the semiconductor device-producing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are laminated is pushed up from the substrate 11 side in the direction from the substrate 11 toward the adhesive layer 12, and the semiconductor device-producing sheet 101 is spread.

In fig. 5B, the non-laminated region where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 is almost parallel to the first surface 13a of the intermediate layer 13, but as described above, in a state in which the non-laminated region is spread by the push-up of the semiconductor device manufacturing sheet 101, the non-laminated region includes an inclined surface whose height gradually decreases as it approaches the outer periphery of the adhesive layer 12 in a direction opposite to the push-up direction.

In this step, by providing the semiconductor device manufacturing sheet 101 with the intermediate layer 13 (in other words, by providing the film-like adhesive 14 before cutting on the intermediate layer 13), the film-like adhesive 14 can be cut at a desired position (in other words, along the outer periphery of the semiconductor chip 9) with good accuracy, and defective cutting can be suppressed.

As shown in fig. 5C, after the spreading, the semiconductor chip 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminated sheet 10 to be picked up.

The pickup at this time can be performed by the same method as the pickup in the manufacturing method 1 described above, and the pickup suitability is also the same as the pickup suitability in the manufacturing method 1.

For example, in this step, when the ratio of the silicon concentration in the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily.

Further, when the intermediate layer 13 contains, for example, an ethylene vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and the ratio of the content of the ethylene vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.

Preferred embodiments of the method for manufacturing a semiconductor chip with a film-like adhesive described above include, for example:

a method for manufacturing a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip,

the sheet for manufacturing a semiconductor device comprises the substrate, an adhesive layer, an intermediate layer, and a film-like adhesive,

the manufacturing method comprises the following steps: a step of forming a modified layer inside a semiconductor wafer by irradiating laser light so as to be focused on a focal point set inside the semiconductor wafer; a step of obtaining a semiconductor chip group in which a plurality of semiconductor chips are aligned by grinding the back surface of the semiconductor wafer on which the modified layer is formed and dividing the semiconductor wafer at a portion on which the modified layer is formed by a force applied to the semiconductor wafer during grinding; a step of attaching the film-like adhesive to the back surfaces of all the semiconductor chips in the semiconductor chip group while heating the semiconductor device manufacturing sheet; a step of obtaining a plurality of semiconductor chip groups with a film-like adhesive, each of which has semiconductor chips with the film-like adhesive aligned on the intermediate layer, by stretching the semiconductor device manufacturing sheet attached to the semiconductor chip groups in a direction parallel to the surface thereof while cooling the sheet, and cutting the film-like adhesive along the outer peripheries of the semiconductor chips; and a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, it may be referred to as "manufacturing method 2").

Although the method of using the semiconductor device-manufacturing sheet 101 shown in fig. 1 has been described as an example of any of the manufacturing methods 1 and 2, the semiconductor device-manufacturing sheet of the present embodiment can be similarly used. In this case, if necessary, the semiconductor device manufacturing sheet may be used by adding other steps as appropriate based on the difference in the structure between the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101.

In addition to the case of the manufacturing method 1 and the manufacturing method 2, after the semiconductor chip group with the film-like adhesive is obtained, the laminated sheet may be extended in a direction parallel to the surface (first surface) of the adhesive layer on the side of the intermediate layer before the semiconductor chip with the film-like adhesive is picked up, and the peripheral edge portion of the semiconductor chip without the film-like adhesive (the semiconductor chip group with the film-like adhesive) in the laminated sheet may be further heated while maintaining this state.

This makes it possible to shrink the peripheral edge portion and to sufficiently widen a distance between adjacent semiconductor chips in the laminated sheet, that is, a notch width, and to maintain the notch width with high uniformity. Further, the semiconductor chip with the film-like adhesive can be picked up more easily.

Examples

The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.

< raw materials for production of adhesive composition >)

The raw materials used to prepare the adhesive composition are shown below.

[ Polymer component (a) ]

(a) -1: an acrylic resin (weight average molecular weight 800000, glass transition temperature 9 ℃) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass).

[ epoxy resin (b1) ]

(b1) -1: an acryl-added cresol novolak type epoxy resin ("CNA 147" manufactured by Nippon Kayaku Co., Ltd., number average molecular weight of 2100, unsaturated group content equal to epoxy group content) having an epoxy equivalent of 518g/eq

[ Heat-curing agent (b2) ]

(b2) -1: aralkyl type phenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals, Inc., number average molecular weight 1100, softening point 63 ℃ C.)

[ Filler (d) ]

(d) -1: spherical silica (YA 050C-MJE manufactured by Admatech corporation, average particle diameter 50nm, methacryl silane-treated product)

[ coupling agent (e) ]

(e) -1: silane coupling agent, 3-glycidyloxypropylmethyldiethoxysilane ("KBE-402" manufactured by Shin-Etsu Chemical Co., Ltd.)

[ crosslinking agent (f) ]

(f) -1: toluene diisocyanate crosslinking agent (CORONATE L, manufactured by TOSOH CORPORATION)

[ example 1]

< production of sheet for semiconductor device production >

< production of base Material >

Low density polyethylene ("SUMIKATHENE L705", manufactured by Sumitomo Chemical co., ltd.) was melted using an extruder, the melt was extruded by a T-die method, and the extrudate was biaxially stretched using a chill roll, thereby obtaining a base material (having a thickness of 110 μm) made of LDPE.

< preparation of adhesive layer >

A non-energy ray-curable adhesive composition containing an acrylic resin (ORIBAIN BPS 6367X manufactured by TOYOCHEM co., ltd.) (100 parts by mass) and a crosslinking agent (byochem co., ltd. "BXX 5640") as an adhesive resin (I-1a) (1 part by mass) was prepared.

Next, using a release film obtained by subjecting one surface of the polyethylene terephthalate film to a release treatment by a silicone treatment, the obtained adhesive composition was applied to the release-treated surface of the release film, and heated and dried at 100 ℃ for 2 minutes, thereby producing a non-energy ray-curable adhesive layer (thickness: 10 μm).

< preparation of intermediate layer >

Ethylene vinyl acetate copolymer (EVA, weight average molecular weight) was reacted at ordinary temperatureA molecular weight of 30000 and a content of structural units derived from vinyl acetate of 25 mass%) (15g) was dissolved in 85g of tetrahydrofuran, and a siloxane-based compound ("polydimethylsiloxane," BYK-333 manufactured by BYK Japan KK., "chemical formula" -Si (-CH) in 1 molecule was added to the solution thus obtained₃)₂The number of the structural units represented by-O- "is 45 to 230) (1.5g), and stirring is carried out to prepare the composition for forming an intermediate layer.

Using a release film obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, the intermediate layer-forming composition obtained above was applied to the release-treated surface of the release film, and heated and dried at 70 ℃ for 5 minutes, thereby producing an intermediate layer (having a thickness of 20 μm).

< preparation of film-shaped adhesive >

A thermosetting adhesive composition containing polymer component (a) -1(100 parts by mass), epoxy resin (b1) -1(10 parts by mass), thermosetting agent (b2) -1(1.5 parts by mass), filler (d) -1(75 parts by mass), coupling agent (e) -1(0.5 part by mass), and crosslinking agent (f) -1(0.5 part by mass) was prepared.

Next, using a release film obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, the adhesive composition obtained above was applied to the release-treated surface of the release film, and heated and dried at 80 ℃ for 2 minutes, thereby producing a thermosetting film-like adhesive (thickness 7 μm).

< production of sheet for semiconductor device production >

The exposed surface of the obtained adhesive layer on the side opposite to the side having the release film was bonded to one surface of the obtained substrate, thereby producing a first intermediate laminate with a release film (in other words, a support sheet with a release film).

A second intermediate laminate with a release film (laminate of a release film, an intermediate layer, a film-like adhesive, and a release film) was produced by laminating the exposed surface of the obtained film-like adhesive on the side opposite to the side provided with the release film to the exposed surface of the obtained intermediate layer on the side opposite to the side provided with the release film.

Then, this second intermediate laminate with a release film was punched out from the release film on the intermediate layer side to the film-shaped adhesive using a cutter blade, and unnecessary portions were removed, thereby producing a second intermediate laminate with a release film, in which a film-shaped adhesive (thickness 7 μm) having a circular planar shape (diameter 305mm), an intermediate layer (thickness 20 μm), and a release film were laminated in this order in the thickness direction on the release film on the film-shaped adhesive side.

Next, the release film was removed from the first intermediate laminate with the release film obtained above, and one surface of the adhesive layer was exposed.

Further, the circular release film was removed from the second processed intermediate laminate with the release film obtained above, and one surface of the intermediate layer was exposed.

Next, the newly generated exposed surface of the adhesive layer in the first intermediate laminate is bonded to the newly generated exposed surface of the intermediate layer in the second intermediate laminate processed product. The base material and the adhesive layer (i.e., the support sheet) in the laminate thus obtained were punched out from the base material side with a cutting blade (diameter: 370mm) so that the planar shape of these (support sheet) was circular (diameter: 370mm) and the circular film-like adhesive and the intermediate layer (diameter: 305mm) were concentric, and unnecessary portions were removed.

Thus, a sheet with a release film for manufacturing a semiconductor device was obtained, which was composed of a substrate (thickness: 110 μm), an adhesive layer (thickness: 10 μm), an intermediate layer (thickness: 20 μm), a film-like adhesive (thickness: 7 μm), and a release film laminated in this order in the thickness direction.

< evaluation of sheet for manufacturing semiconductor device >

< calculation of the ratio of silicon concentration on the surface of the intermediate layer on the film-shaped pressure-sensitive adhesive side >

In the process of manufacturing the semiconductor device manufacturing sheet, XPS analysis was performed on the exposed surface of the intermediate layer at the stage before the intermediate layer was bonded to the adhesive layer, and the concentrations (atomic%) of carbon (C), oxygen (O), nitrogen (N), and silicon (Si) were measured, and from the measured values, the ratio (%) of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon was obtained.

XPS analysis Using an X-ray photoelectron spectroscopy apparatus ("Quantra SXM" manufactured by ULVAC, Inc.) and an X-ray beam diameter at an irradiation angle of 45%

The output was 4.5W. The results are shown in the column "proportion (%) of element concentration in the intermediate layer" in table 1 together with the proportion (%) of concentration of other elements.

< evaluation of the effect of suppressing the generation of chips when cutting with a blade >

[ production of silicon chip set with film adhesive ]

The release film in the semiconductor device-manufacturing sheet obtained as described above was removed.

The semiconductor device-manufacturing sheet was bonded to the back surface (polished surface) of a silicon wafer (diameter 300mm and thickness 75 μm) whose back surface was polished by dry polishing, while being heated to 60 ℃ by a tape bonder ("adwire RAD 2500" manufactured by Lintec Corporation). In this way, a laminate (a laminate in which the laminate sheet, the film-like adhesive, and the silicon wafer are laminated in this order in the thickness direction) is obtained, the laminate being formed by laminating a substrate, an adhesive layer, an intermediate layer, a film-like adhesive, and a silicon wafer in this order in the thickness direction.

Next, a region (the non-laminated region) in the vicinity of the peripheral edge portion of the first surface of the adhesive layer in the laminated body, on which the intermediate layer is not provided, is fixed to the ring frame for dicing.

Subsequently, the silicon wafer was divided by dicing using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), and the film-like adhesive was also cut to obtain silicon chips having a size of 8mm × 8 mm. The cutting at this time was performed in the following manner: the rotation speed of the blade was 30000rpm, and the moving speed of the blade was 30 mm/sec, and the blade was cut into the middle region of the intermediate layer from the adhesion surface of the film-like adhesive of the silicon wafer (i.e., the entire region in the thickness direction of the film-like adhesive and the region from the surface of the intermediate layer on the film-like adhesive side to the middle) with respect to the sheet for semiconductor device fabrication. As the blade, "Z05-SD 2000-D1-90 CC" manufactured by DISCO Corporation was used.

Thus, a silicon chip group with a film-like adhesive was obtained, which was provided with a plurality of silicon chips with a film-like adhesive provided on the back surface thereof and the film-like adhesive after cutting, in a state in which the silicon chips were aligned and fixed to the intermediate layer in the laminate sheet by the film-like adhesive.

[ evaluation of the Effect of suppressing the production of chips ]

The obtained silicon chip group with a film-like pressure-sensitive adhesive was observed from above on the silicon chip side thereof using a digital microscope ("VH-Z100" manufactured by KEYENCE CORPORATION) to confirm whether or not cutting chips were generated. Further, the case where no chips were generated was determined as "a", and the case where chips were generated even in a small amount was determined as "B". The results are shown in Table 1.

< evaluation of cuttability of film-shaped adhesive during expansion >

[ production of silicon chip set with film adhesive ]

A silicon wafer having a circular planar shape with a diameter of 300mm and a thickness of 775 μm was used, and a back grinding tape ("Adwill E-3100 TN" manufactured by LINTEC Corporation) was attached to one surface of the silicon wafer.

Next, a laser irradiation apparatus ("DFL 73161" manufactured by DISCO Corporation) was used to irradiate laser light so as to be focused at a focal point set inside the silicon wafer, thereby forming a modified layer inside the silicon wafer. In this case, the focal point is set so that a plurality of silicon chips having a size of 8mm × 8mm can be obtained from the silicon wafer. Further, the silicon wafer was irradiated with laser light from the other surface (surface to which the back grind tape was not attached) side of the silicon wafer.

Next, the other surface of the silicon wafer was polished by a grinder to make the thickness of the silicon wafer 30 μm, and the silicon wafer was divided at the site where the modified layer was formed by the force applied to the silicon wafer at the time of polishing, thereby forming a plurality of silicon chips. Thus, a silicon chip set in which a plurality of silicon chips are aligned and fixed to a back-grinding tape was obtained.

Next, one of the semiconductor device manufacturing sheets obtained above was heated to 60 ℃ and the film-like adhesive was attached to the other surface (in other words, the polished surface) of all the silicon chips (silicon chip groups) using a tape laminator ("Adwill RAD 2500" manufactured by LINTEC Corporation).

Next, a region (the non-laminated region) in the vicinity of the peripheral edge portion where the intermediate layer is not provided in the first surface of the adhesive layer in the semiconductor device manufacturing sheet bonded to the silicon chip group is fixed to the ring frame for dicing.

Next, the back grinding tape was removed from the silicon chip group in the fixed state. Then, the semiconductor device-manufacturing sheet was spread in a direction parallel to the surface thereof while being cooled in an environment of 0 ℃ using a full-automatic die bonder ("DDS 2300" manufactured by DISCO Corporation), thereby cutting the film-like adhesive along the outer periphery of the silicon chip. At this time, the peripheral edge portion of the semiconductor device-manufacturing sheet was fixed, and the entire region of the semiconductor device-manufacturing sheet on which the intermediate layer and the film-like adhesive were laminated was pushed up by only 15mm from the substrate side of the semiconductor device-manufacturing sheet, thereby spreading the sheet.

Thus, a silicon chip group with a film-like pressure-sensitive adhesive was obtained, which was provided with a plurality of silicon chips with a film-like pressure-sensitive adhesive provided on the other surface (polished surface) of the silicon chip, and which was fixed in alignment to the intermediate layer.

Next, after the spread of the semiconductor device manufacturing sheet is once released, a laminated body (that is, the laminated sheet) formed by laminating the base material, the adhesive agent layer, and the intermediate layer is spread in a direction parallel to the first surface of the adhesive agent layer at normal temperature. Further, the spread state is maintained, and the peripheral edge portion of the silicon chip on which the adhesive with a film shape is not mounted in the laminated sheet is heated. Thereby, the peripheral portion is contracted, and the width of the slit between the adjacent silicon chips in the laminated sheet is kept at a certain value or more.

[ evaluation of cuttability of film-shaped adhesive ]

In the production of the silicon chip set with the film-like pressure-sensitive adhesive, the obtained silicon chip set with the film-like pressure-sensitive adhesive was observed from above on the silicon chip side thereof using a digital microscope ("VH-Z100" manufactured by KEYENCE CORPORATION). Then, the number of cutting lines that are not actually formed and the number of cutting lines that are incomplete out of the plurality of cutting lines of the film-like adhesive extending in one direction and the plurality of cutting lines of the film-like adhesive extending in a direction orthogonal to the one direction, which are to be formed when the film-like adhesive is supposed to be normally cut by spreading of the semiconductor device manufacturing sheet, were confirmed, and the cuttability of the film-like adhesive was evaluated according to the following evaluation criteria.

The results are shown in Table 1.

(evaluation criteria)

A: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the film-shaped adhesive which is not completely formed is 5 or less.

B: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the incomplete film-shaped adhesive is more than 6.

< evaluation of pickup Property of silicon chip with film-shaped adhesive after expansion >

After the evaluation of the cuttability of the film-like adhesive, the silicon chip with the film-like adhesive was picked up from the intermediate layer in the laminated sheet under the conditions of a push-up height of 250 μm, a push-up speed of 5mm/s, and a push-up time of 500ms using a silicon chip set with a film-like adhesive and a die bonder ("PU 100" manufactured by fafford TECHNOLOGY co. Further, a case where all the silicon chips with the film-like adhesive could be picked up normally was evaluated as "a", and a case where 1 or more silicon chips with the film-like adhesive could not be picked up normally was evaluated as "B". The results are shown in Table 1.

< measurement of T-type peel Strength between intermediate layer and film-shaped adhesive >

The release film on the semiconductor device manufacturing sheet obtained above was removed.

The entire exposed surface of the film-like adhesive in the thus produced sheet for manufacturing a semiconductor device was bonded to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET 50(a) PL シン 8 LK" manufactured by Lintec Corporation), and the thus obtained laminate was cut into a size of 50mm × 100mm, thereby producing a test sheet.

The test piece was peeled in a T-shape by pulling a laminate of the substrate, the adhesive layer and the intermediate layer (that is, the laminate), a laminate of the film-like adhesive and the adhesive tape, according to JIS K6854-3, and the maximum value of the peel force (mN/50mm) measured at this time was defined as the T-type peel strength. At this time, the peeling rate was measured under the condition of 50 mm/min. The results are shown in Table 1.

< production and evaluation of sheet for producing semiconductor device >)

[ example 2]

A semiconductor device-manufacturing sheet was produced and evaluated in the same manner as in example 1, except that the amount of the intermediate layer-forming composition applied was increased to make the thickness of the intermediate layer 80 μm instead of 20 μm. The results are shown in Table 1.

[ example 3]

A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that the siloxane compound was not added when the intermediate layer-forming composition was prepared, and the amount of the ethylene-vinyl acetate copolymer was set to 16.5g instead of 15g (in other words, only the ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran by using the same mass of the ethylene-vinyl acetate copolymer instead of the siloxane compound). 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

A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that, in the preparation of the intermediate layer-forming composition, the same mass of an ethylene vinyl acetate copolymer (EVA, weight average molecular weight 200000, content of structural units derived from vinyl acetate 25 mass%) was used in place of the ethylene vinyl acetate copolymer, and the coating amount of the intermediate layer-forming composition was increased so that the thickness of the intermediate layer was 80 μm instead of 20 μm. The results are shown in Table 1.

Comparative example 2

A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that the same mass of an ethylene vinyl acetate copolymer (EVA, weight average molecular weight of 200000, content of structural units derived from vinyl acetate of 25 mass%) was used in place of the ethylene vinyl acetate copolymer in the preparation of the intermediate layer-forming composition. The results are shown in Table 1.

[ Table 1]

From the above results, it is understood that in examples 1 to 3, the generation of cutting chips is suppressed when dicing is performed, and the cutting failure of the film-like adhesive is suppressed when spreading is performed, and the suitability for dividing the semiconductor wafer is excellent.

In examples 1 to 3, the weight average molecular weight of the ethylene vinyl acetate copolymer contained as a main component in the intermediate layer in the sheet for manufacturing a semiconductor device was 30000.

In examples 1 to 3, the content of the ethylene-vinyl acetate copolymer in the intermediate layer was 90.9 mass% or more with respect to the total mass of the intermediate layer, and the content of the siloxane-based compound was 9.1 mass% or less with respect to the total mass of the intermediate layer.

In addition, in examples 1 to 2, the silicon chips with the film-like adhesive after spreading were excellent in pickup properties.

In examples 1 to 2, the T-peel strength between the intermediate layer and the film-like adhesive was 100mN/50mm or less, which was moderately low, and the silicon concentration ratio of the intermediate layer was 9%, which was moderately high. These evaluation results were in agreement with the evaluation results of the above-described pickup property of the silicon chip with a film-like pressure-sensitive adhesive.

In example 3, the intermediate layer in the semiconductor device-producing sheet did not contain the siloxane compound.

Although the semiconductor device-manufacturing sheets of examples 1 to 2 differ only in the thickness of the intermediate layer, the T-peel strength between the intermediate layer and the film-like adhesive of the semiconductor device-manufacturing sheet of example 2 was smaller than that of the semiconductor device-manufacturing sheet of example 1, and the pickup of the silicon chip with the film-like adhesive of example 2 was easier than that of example 1. This is presumably because, even though the proportion (% by mass) of the siloxane compound content in the intermediate layer to the total mass of the intermediate layer was the same in the semiconductor device-manufacturing sheets of examples 1 to 2, the amount of the siloxane compound unevenly distributed on both surfaces of the intermediate layer and in the vicinity thereof in example 2 was larger than in example 1 because the siloxane compound content (parts by mass) in the intermediate layer in example 2 was more likely to unevenly distribute on both surfaces of the intermediate layer and in the vicinity thereof in the intermediate layer than in example 1.

In examples 1 to 3, no nitrogen was detected by XPS analysis of the exposed surface of the intermediate layer.

On the other hand, in comparative examples 1 to 2, the generation of chips was not suppressed during the dicing operation, and the suitability for dividing the semiconductor wafer was poor.

In comparative examples 1 to 2, the weight average molecular weight of the ethylene vinyl acetate copolymer contained as a main component in the intermediate layer in the sheet for manufacturing a semiconductor device was 200000.

The semiconductor device-manufacturing sheets of comparative examples 1 to 2 differ only in the thickness of the intermediate layer, and the T-peel strength relationship between the intermediate layer and the film-like adhesive in comparative examples 1 to 2 tends to be the same as in examples 1 to 2.

In comparative examples 1 to 2, no nitrogen was detected when the exposed surface of the intermediate layer was analyzed by XPS.

Industrial applicability

The invention can be used for manufacturing semiconductor devices.

Description of the reference numerals

101: a semiconductor device manufacturing sheet; 11: a substrate; 12: an adhesive layer; 13: an intermediate layer; 13 a: a first side of the intermediate layer; 14: a film-like adhesive.

Claims (3)

1. A sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component.

2. The semiconductor device-manufacturing sheet according to claim 1, wherein,

when the surface of the intermediate layer on the film-like binder side is analyzed by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon is 1 to 20%.

3. The semiconductor device-manufacturing sheet according to claim 1 or 2,

the intermediate layer contains an ethylene-vinyl acetate copolymer and a silicone compound as the non-silicone resin,

in the 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 to 40% by mass,

in the intermediate layer, the content of the ethylene-vinyl acetate copolymer is 90 to 99.99 mass% relative to the total mass of the intermediate layer,

in the intermediate layer, the ratio of the content of the siloxane compound to the total mass of the intermediate layer is 0.01-10 mass%.

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