KR20220155978A - Sheets for manufacturing semiconductor devices - Google Patents

Abstract

A substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film adhesive are provided, and the pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the substrate, and the intermediate layer has a weight average molecular weight A sheet for manufacturing a semiconductor device containing the non-silicon resin of 100,000 or less as a main component.

Description

Sheets for manufacturing semiconductor devices

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

This application claims priority based on Japanese Patent Application No. 2020-058734 for which it applied to Japan on March 27, 2020, and uses the content here.

BACKGROUND OF THE INVENTION [0002] In the manufacture of a semiconductor device, a semiconductor chip formed with a film adhesive comprising a semiconductor chip and a film adhesive formed on the back surface thereof is used.

As an example of the manufacturing method of the semiconductor chip with a film adhesive, what is shown below is mentioned, for example.

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

Examples of the dicing die-bonding sheet include a support sheet and a film adhesive formed on one side of the support sheet, and the support sheet can be used as a dicing sheet. Examples of the support sheet include those provided with a base material and an adhesive layer formed on one side of the base material; There are multiple types of things having different configurations, such as those composed only of a base material. As for the support sheet provided with the adhesive layer, the outermost surface at the side of the adhesive layer becomes the surface on which the film adhesive is formed. The dicing die bonding sheet is attached to the back surface of the semiconductor wafer with the film adhesive in it.

Next, by blade dicing, the semiconductor wafer and film adhesive on the support sheet are cut together. "Cutting" of a semiconductor wafer is also referred to as "division", whereby the semiconductor wafer is divided into target semiconductor chips. The film adhesive is cut along the periphery of the semiconductor chip. While this obtains a semiconductor chip with a film adhesive provided with a semiconductor chip and a film adhesive after cutting formed on its back surface, a semiconductor chip with a plurality of these film adhesives is aligned on a support sheet A semiconductor chip group formed with a film adhesive, which is maintained and configured, is obtained.

Next, the semiconductor chip on which the film adhesive is formed is separated from the support sheet and picked up. In the case of using a support sheet with a curable pressure-sensitive adhesive layer, pick-up becomes easy by curing the pressure-sensitive adhesive layer at this time to lower the adhesiveness.

By the above, the semiconductor chip with the film adhesive used for manufacture of a semiconductor device is obtained.

As another example of the manufacturing method of the semiconductor chip with a film adhesive, what is shown below is mentioned, for example.

That is, first, back grind tape (also referred to as "surface protection tape") is affixed to the circuit formation surface of the semiconductor wafer.

Next, inside the semiconductor wafer, a portion to be divided is set, and a region included in the portion is set as a focal point, and a laser beam is irradiated so as to focus on the focal point, thereby forming a modified layer inside the semiconductor wafer. Then, while adjusting the thickness of the semiconductor wafer to a target value by grinding the back side of the semiconductor wafer using a grinder, forming a modified layer by using the force applied to the semiconductor wafer at the time of grinding at this time In the site, a semiconductor wafer is divided (individualized) to produce a plurality of semiconductor chips. The method of dividing a semiconductor wafer involving the formation of a modified layer in this way is called stealth dicing (registered trademark). It is essentially completely different from laser dicing, which cuts from the surface.

Next, one die bonding sheet is affixed to the back surface (in other words, the ground surface) on which all of these semiconductor chips fixed on the back grind tape have been ground and ground. As a die bonding sheet, the same thing as the said dicing die bonding sheet is mentioned. In this way, there are cases in which the die bonding sheet can be designed to have the same configuration as that of the dicing die bonding sheet, except that it is not used for dicing of semiconductor wafers. A die bonding sheet is also attached to the back surface of the semiconductor chip with the film adhesive in it.

Then, after removing the back grind tape from the semiconductor chip, the die bonding sheet is stretched in a direction parallel to the surface (for example, the sticking surface of the film adhesive to the semiconductor chip) while cooling, so-called expand (cool Expand), the film adhesive is cut along the outer periphery of the semiconductor chip.

By the above, the semiconductor chip with the film adhesive provided with the semiconductor chip and the film adhesive after cutting formed on the back surface is obtained.

Next, similarly to the case where the blade dicing is employed, the semiconductor chip with the film adhesive used for manufacturing the semiconductor device is obtained by separating and picking up the semiconductor chip with the film adhesive from the support sheet.

Both the dicing die-bonding sheet and the die-bonding sheet can be used for production of a semiconductor chip on which a film adhesive is formed, and finally enables production of a target semiconductor device. In this specification, a dicing die-bonding sheet and a die-bonding sheet are collectively referred to as a "semiconductor device manufacturing sheet".

As a sheet for manufacturing semiconductor devices, for example, a dicing die bonding tape having a structure in which a substrate layer (corresponding to the above support sheet) and an adhesive layer (corresponding to the above film adhesive) are laminated in direct contact with each other (the above dicing die). Equivalent to a bonding sheet) is disclosed (see Patent Document 1). In this dicing die bonding tape, since the 90-degree peeling force at -15°C of the base material layer and the adhesive layer is adjusted to a specific range, the adhesive layer can be precisely divided by expanding, and the base material Since the 90 degree peeling force at 23°C of the layer and the adhesive layer is adjusted to a specific range, when this dicing die bonding tape is used, a semiconductor chip with an adhesive layer (corresponding to the semiconductor chip with the film adhesive) It is said that it is possible to pick up without difficulty, and to suppress separation of semiconductor wafers and semiconductor chips from the adhesive layer in the process up to pick-up.

Japanese Unexamined Patent Publication No. 2018-56289

However, the dicing die bonding tape disclosed in Patent Literature 1 is suitable for application to stealth dicing (registered trademark), but is not suitable for application to blade dicing. When blade dicing is performed using this dicing die bonding tape, whisker-like cutting chips (in the art, sometimes referred to as "whisker" or the like) are easily generated from the substrate layer, and the semiconductor wafer is divided. The divisional aptitude when doing it was poor.

An object of the present invention is to provide a sheet for semiconductor device manufacture having excellent splitting ability of semiconductor wafers.

The present invention includes a substrate, an adhesive layer, an intermediate layer, and a film adhesive, and is configured by stacking the adhesive layer, the intermediate layer, and the film adhesive in this order on the substrate, wherein the intermediate layer, A sheet for manufacturing a semiconductor device containing, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less.

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

In the sheet for manufacturing a semiconductor device of the present invention, the intermediate layer contains the ethylene-vinyl acetate copolymer, which is the non-silicon-based resin, and a siloxane-based compound, and in the ethylene-vinyl acetate copolymer, with respect to the total mass of all constituent units, The ratio of the mass of structural units derived from vinyl acetate is 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 is 90 to 99.99% by mass, and In the intermediate layer, the ratio of the content of the siloxane-based compound to the total mass of the intermediate layer may be 0.01 to 10% by mass.

ADVANTAGE OF THE INVENTION According to this invention, the sheet|seat for semiconductor device manufacture excellent in the splitting ability of a semiconductor wafer is provided.

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

◇Seat for semiconductor device manufacturing

A sheet for manufacturing a semiconductor device according to an embodiment of the present invention includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film adhesive, and the pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are disposed on the substrate in this order. , and the intermediate layer contains, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less.

When blade dicing is performed using the sheet for manufacturing semiconductor device of the present embodiment as a dicing die bonding sheet, the sheet for manufacturing semiconductor device has the intermediate layer, so that the blade can easily reach the base material. It can be avoided, and the generation of whisker-like cutting chips (alias: Whisker, hereinafter sometimes referred to simply as “cutting chips” without being limited to those derived from the base material) from the base material can be suppressed. . Further, the main component of the intermediate layer cut by the blade is a non-silicon-based resin having a weight average molecular weight of 100,000 or less, particularly, when the weight average molecular weight is 100,000 or less, the generation of cutting chips from the intermediate layer can also be suppressed.

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 sheet for semiconductor device manufacturing of the present embodiment as a die bonding sheet, the semiconductor device manufacturing Since the sheet is provided with the above-mentioned intermediate layer, the sheet for semiconductor device production is subsequently stretched in a direction parallel to the surface (for example, the sticking surface of the film adhesive to the semiconductor chip), by performing so-called expand , The film adhesive is precisely cut at the target location, and cutting defects can be suppressed.

Thus, the semiconductor device manufacturing sheet of the present embodiment suppresses the generation of cutting chips from the base material and the intermediate layer during blade dicing, and suppresses cutting defects of the film adhesive during the expansion. It has a property of suppressing the occurrence of problems during wafer division, and has excellent semiconductor wafer division aptitude.

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

A method of using the sheet for semiconductor device manufacture of the present embodiment will be described in detail later.

Hereinafter, the sheet for semiconductor device manufacture of this embodiment is explained in detail, referring drawings. On the other hand, in the drawings used in the following description, in order to make the characteristics of the present invention easier to understand, there are cases where the main parts are enlarged and shown for convenience, and the dimensional ratio of each component is not limited to being the same as the actual one. don't

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

On the other hand, in the drawings subsequent to Fig. 2, the same reference numerals as those in the previously described drawings are assigned the same reference numerals, and detailed descriptions thereof are omitted.

The sheet|seat 101 for semiconductor device manufacture shown here is equipped with the base material 11, and the adhesive layer 12, the intermediate|middle layer 13, and the film adhesive 14 are laminated|stacked in this order on the base material 11, Consists of. The sheet 101 for semiconductor device manufacture is further on the opposite side to the side where the intermediate layer 13 of the film adhesive 14 is formed (hereinafter sometimes referred to as "the first surface") 14a A peeling film 15 is provided.

In the sheet 101 for semiconductor device manufacture, an adhesive layer 12 is formed on one surface (in this specification, it may be referred to as “first surface”) 11a of the base material 11, and the adhesive layer The intermediate layer 13 is formed on the surface (in this specification, sometimes referred to as the “first surface”) 12a opposite to the side on which the base material 11 of (12) is formed, and the intermediate layer 13 ) The film adhesive 14 is formed on the side opposite to the side on which the pressure-sensitive adhesive layer 12 is formed (in this specification, it may be referred to as "the first surface") 13a, A release film 15 is formed on the first surface 14a of the adhesive 14 . Thus, the sheet|seat 101 for semiconductor device manufacture is comprised by the base material 11, the adhesive layer 12, the intermediate|middle layer 13, and the film adhesive 14 laminated|stacked in this order in these thickness directions. .

The sheet|seat 101 for semiconductor device manufacture is the state in which the release film 15 was removed, and the 1st surface 14a of the film adhesive 14 in it is a semiconductor wafer, a semiconductor chip, or a semiconductor wafer which is not completely divided. (not shown) is attached to the back side and used.

In this specification, in both cases of a semiconductor wafer and a semiconductor chip, the surface on which the circuit is formed is referred to as a "circuit formation surface", and the surface opposite to the circuit formation surface is referred to as a "rear surface".

In this specification, a laminate having a structure in which a base material and an adhesive layer are laminated in their thickness direction and an intermediate layer is not laminated is sometimes referred to as a "support sheet". In Fig. 1, reference numeral 1 is given to indicate the support sheet.

In addition, a laminate having a configuration in which a base material, an adhesive layer, and an intermediate layer are laminated in this order in the thickness direction may be referred to as a "laminated sheet". In Fig. 1, reference numeral 10 is given to indicate a laminated sheet. The laminate of the support sheet and the intermediate layer is included in the laminate sheet.

The planar shapes of the intermediate layer 13 and the film adhesive 14 when viewed from above as viewed from above are all circular, and the diameter of the intermediate layer 13 and the diameter of the film adhesive 14 are the same .

And in the sheet|seat 101 for semiconductor device manufacture, the intermediate|middle layer 13 and the film adhesive 14 are so that these centers may coincide, in other words, the position of the outer periphery of the intermediate layer 13 and the film adhesive 14 is All of them are arranged so as to coincide in the diametrical direction.

Both the first surface 13a of the intermediate layer 13 and the first surface 14a of the film adhesive 14 have a smaller area than the first surface 12a of the pressure-sensitive adhesive layer 12 . And the maximum value (ie, diameter) of the width (W ₁₃ ) of the intermediate layer 13 and the maximum value (ie, diameter) of the width (W ₁₄ ) of the film adhesive 14 are both the pressure-sensitive adhesive layer 12 It is smaller than the maximum value of the width of and the maximum value of the width of the substrate 11. Therefore, in the sheet|seat 101 for semiconductor device manufacture, a part of 1st surface 12a of the adhesive layer 12 is not covered with the intermediate|middle layer 13 and the film adhesive 14. In such a region on the first surface 12a of the pressure-sensitive adhesive layer 12, where the intermediate layer 13 and the film adhesive 14 are not laminated, the release film 15 is directly contacted and laminated, In the state where the peeling film 15 is removed, this area|region is exposed (Hereinafter, in this specification, this area|region may be called "non-lamination area|region").

On the other hand, in the sheet|seat 101 for semiconductor device manufacture provided with the peeling film 15, the area|region which is not covered with the intermediate|middle layer 13 and the film adhesive 14 of the adhesive layer 12 is as shown here Similarly, there may or may not be a region where the release film 15 is not laminated.

The film adhesive 14 is uncut, and the sheet 101 for semiconductor device manufacture in a state where it is adhered to the above-mentioned semiconductor wafer or semiconductor chip or the like by the film adhesive 14, in the pressure-sensitive adhesive layer 12 therein It can be fixed by attaching a part of said non-lamination area|region to a jig, such as a ring frame for fixing a semiconductor wafer. Therefore, it is not necessary to separately form the adhesive layer for a jig for fixing the sheet 101 for semiconductor device manufacture to the jig on the sheet 101 for semiconductor device manufacture. And since there is no need to form a jig adhesive layer, the sheet 101 for semiconductor device manufacture can be manufactured efficiently at low cost.

Thus, although the sheet|seat 101 for semiconductor device manufacture shows an advantageous effect by not providing a jig adhesive layer, you may be equipped with the jig adhesive agent layer. In this case, the jig adhesive layer is formed in a region near the periphery of the surface of a certain layer constituting the sheet 101 for semiconductor device manufacture. As such an area, the above non-laminated area in the first surface 12a of the pressure-sensitive adhesive layer 12 and the like are exemplified.

The jig adhesive layer may be a known one, and may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material.

In addition, as will be described later, when the sheet 101 for semiconductor device manufacture is stretched in a direction parallel to the surface (for example, the first surface 12a of the pressure-sensitive adhesive layer 12), so-called expansion is performed. , When the non-laminated region exists on the first surface 12a of the pressure-sensitive adhesive layer 12, the sheet 101 for semiconductor device manufacture can be easily expanded. And not only the film adhesive 14 can be easily cut, but also the peeling of the intermediate layer 13 and the film adhesive 14 from the pressure-sensitive adhesive layer 12 is suppressed.

In the sheet|seat 101 for semiconductor device manufacture, the intermediate|middle layer 13 contains a non-silicon resin whose weight average molecular weight is 100000 or less as a main component.

The semiconductor device manufacturing sheet of the present embodiment is not limited to those shown in Figs. 1 and 2, and some of the configurations of those shown in Figs. 1 and 2 are changed, deleted, and Or it may be added.

For example, the sheet for semiconductor device manufacture of the present embodiment includes a base material, an adhesive layer, an intermediate layer, a film adhesive, a peeling film, and other layers that do not correspond to any of the jig adhesive layer, There may be. However, as shown in Fig. 1, the sheet for semiconductor device manufacture of the present embodiment includes a pressure-sensitive adhesive layer in direct contact with the base material and an intermediate layer in direct contact with the pressure-sensitive adhesive layer, and a film adhesive is applied to the intermediate layer. It is preferable to provide in a state of direct contact.

For example, in the semiconductor device manufacturing sheet of the present embodiment, the plane shape of the intermediate layer and the film adhesive may be a shape other than circular, and the plane shape of the intermediate layer and the film adhesive may be the same or different. Further, both the area of the first surface of the intermediate layer and the area of the first surface of the film adhesive are preferably smaller than the area of the surface of the base material side layer (for example, the first surface of the pressure-sensitive adhesive layer), They may be the same as or different from each other. And the position of the outer periphery of an intermediate|middle layer and a film adhesive may or may not all coincide in these radial directions.

Next, each layer constituting the sheet for semiconductor device manufacture of the present embodiment will be described in more detail.

○Remarks

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

It is preferable that the constituent material of the base material is various resins, specifically, for example, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene (PP) , polybutene, polybutadiene, polymethylpentene, styrene ethylenebutylene styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, Polyurethane acrylate, polyimide (PI), ionomer resin, ethylene/(meth)acrylic acid copolymer, ethylene/(meth)acrylic acid ester copolymer, ethylene/(meth)acrylic acid copolymer, and ethylene/(meth)acrylic acid ester Ethylene copolymers other than copolymers, polystyrene, polycarbonate, fluororesins, and hydrogenated products, modified products, crosslinked products, or copolymers of any one of these resins are exemplified.

In addition, in this specification, "(meth)acrylic acid" is taken as the concept containing both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth)acryloyl group " is a concept including both "acryloyl group" and "methacryloyl group".

The resin constituting the substrate may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The base material may consist of one layer (single layer) or may consist of a plurality of layers of two or more layers. When the base material consists of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

In this specification, not limited to the case of description, "a plurality of layers may be the same as or different from each other", "all layers may be the same, all layers may be different, and only some of the layers may be the same" and "a plurality of layers are different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other".

The thickness of the substrate can be appropriately selected depending on the purpose, but it is preferably 50 to 300 μm, and more preferably 60 to 150 μm. When the thickness of the substrate is equal to or greater than the lower limit, the structure of the substrate is further stabilized. When the thickness of the substrate is equal to or less than the above upper limit, the film adhesive can be more easily cut at the time of blade dicing and the above expansion of the sheet for semiconductor device manufacture.

Here, "thickness of a base material" means the thickness of the whole base material, and, for example, the thickness of a base material consisting of a plurality of layers means the total thickness of all the layers constituting the base material.

In order to improve adhesion with other layers such as an adhesive layer formed thereon, the base material is subjected to roughening treatment by sandblasting treatment, solvent treatment, embossing treatment or the like; oxidation treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet radiation treatment, flame treatment, chromic acid treatment, and hot air treatment; etc. may be given to the surface.

The surface of the substrate may be subjected to primer treatment.

The substrate may include an antistatic coat layer; a layer that prevents the substrate from adhering to another sheet or the substrate from adhering to the adsorption table when the die bonding sheets are stacked and stored; You may have your back.

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

The optical properties of the substrate are not particularly limited within a range that does not impair the effects of the present invention. The substrate may transmit, for example, laser light or energy rays.

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

○Adhesive layer

The pressure-sensitive adhesive layer is in the form of a sheet or film and contains an adhesive.

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on the target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying as necessary.

In the pressure-sensitive adhesive layer, the ratio of the total content of one or two or more of the later-described components of the pressure-sensitive adhesive layer to the total mass of the pressure-sensitive adhesive layer does not exceed 100% by mass.

Similarly, in the pressure-sensitive adhesive composition, the ratio of the total content of one or two or more of the later-described components of the pressure-sensitive adhesive composition to the total mass of the pressure-sensitive adhesive composition does not exceed 100% by mass.

Coating of the pressure-sensitive adhesive composition may be performed by a known method, and examples thereof include an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, and a Mayer bar. A method using various coaters such as a coater and a kiss coater is exemplified.

Drying conditions for the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat-dry the pressure-sensitive adhesive composition, and in this case, for example, at 70 to 130 ° C. Drying is preferred.

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ether, polycarbonate, and ester-based resins, and acrylic resins are preferable.

In the present specification, "adhesive resin" includes both resins having adhesiveness and resins having adhesiveness. For example, in the above-mentioned adhesive resin, a resin that not only has adhesiveness by itself but also exhibits adhesiveness when used in combination with other components such as additives, or a resin that exhibits adhesiveness by the presence of a trigger such as heat or water. etc. are also included.

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

In this specification, an "energy ray" means one having energy quanta in an electromagnetic wave or a charged particle beam. Examples of energy rays include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. Electron beams generated by an electron beam accelerator or the like can be irradiated.

In addition, in this specification, “energy ray curability” means a property that is cured by irradiation with energy rays, and “non-energy ray curability” means a property that is not cured even when irradiated with energy rays.

The pressure-sensitive adhesive layer may consist of one layer (single layer) or may consist of a plurality of layers of two or more layers. It doesn't work.

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

Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.

The optical properties of the pressure-sensitive adhesive layer are not particularly limited within a range that does not impair the effects of the present invention. For example, the pressure-sensitive adhesive layer may transmit energy rays.

Next, the pressure-sensitive adhesive composition will be described.

<<Adhesive composition>>

When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, is, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, "adhesive resin (I-1a)” may be abbreviated) and an energy ray-curable compound (I-1); Energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") containing Pressure-sensitive adhesive composition (I-2); The adhesive composition (I-3) containing the said adhesive resin (I-2a) and an energy ray-curable compound, etc. are mentioned.

<Adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth)acrylic-acid alkylester at least is mentioned, for example.

1 type of structural unit which the said acrylic resin has may be sufficient as it, and 2 or more types may be sufficient as it. In the case of 2 or more types, these combination and ratio can be arbitrarily selected.

The adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by energy ray irradiation.

Among the energy ray-curable compounds, as a monomer, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ) Polyvalent (meth)acrylates such as acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; Epoxy (meth)acrylate etc. are mentioned.

Among the energy ray-curable compounds, examples of the oligomer include oligomers formed by polymerization of the above-exemplified monomers.

The energy ray-curable compound has a relatively large molecular weight and is preferably urethane (meth)acrylate or urethane (meth)acrylate oligomer from the viewpoint of being difficult to reduce the storage modulus of the pressure-sensitive adhesive layer.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass, and preferably 5 to 90% by mass. It is more preferable, and it is especially preferable that it is 10-85 mass %.

[Crosslinking agent]

As the adhesive resin (I-1a), in the case of using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth)acrylic acid, the adhesive composition (I-1) further comprises: It is preferable to contain a crosslinking agent.

The crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a).

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

It is preferable that the crosslinking agent is an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the pressure-sensitive adhesive layer and easy availability.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the case of using a crosslinking agent, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the adhesive resin (I-1a). It is more preferable, and it is especially preferable that it is 0.3-15 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the adhesive composition (I-1) containing a photoinitiator is irradiated with relatively low-energy energy rays, such as an ultraviolet-ray, a hardening reaction fully advances.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. benzoin compounds; 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 bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloro anthraquinone etc. are mentioned.

Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 to 20 parts by mass, and preferably 0.03 to 10 parts by mass with respect to 100 parts by mass of the energy ray-curable compound. It is more preferable, and it is especially preferable that it is 0.05-5 mass parts.

[Other additives]

The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, tackifiers, reaction retardants, crosslinking accelerators ( catalyst) and other known additives.

The reaction retardant is, for example, used to suppress an undesired crosslinking reaction from proceeding in the PSA composition (I-1) during storage by the action of a catalyst incorporated in the PSA composition (I-1). is an ingredient for Examples of the reaction retardant include those that form a chelate complex by chelating the catalyst, and more specifically, those having two or more carbonyl groups (-C(=O)-) in one molecule. can

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

The content of other additives in the PSA composition (I-1) is not particularly limited, and may be appropriately selected according to the type.

[menstruum]

The pressure-sensitive adhesive composition (I-1) may contain a solvent. By containing a solvent, the pressure-sensitive adhesive composition (I-1) improves the coating aptitude to the surface to be coated.

It is preferable that the said solvent is an organic solvent.

<Adhesive composition (I-2)>

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

[Adhesive resin (I-2a)]

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

The compound containing an unsaturated group is a compound having a group capable of bonding to the adhesive resin (I-1a) by further 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 (ethenyl group), an allyl group (2-propenyl group), and the like, with a (meth)acryloyl group being preferable. .

Examples of groups capable of bonding with functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding with hydroxyl groups or amino groups, hydroxyl groups and amino groups capable of bonding with carboxy groups or epoxy groups, and the like.

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 pressure-sensitive adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

[Crosslinking agent]

As the adhesive resin (I-2a), for example, when the acrylic polymer having the same structural units derived from the functional group-containing monomer as in the adhesive resin (I-1a) is used, the adhesive composition (I-2) may further contain a crosslinking agent.

Examples of the crosslinking agent in the PSA composition (I-2) include the same crosslinking agent in the PSA composition (I-1).

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the case of using a crosslinking agent, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the adhesive resin (I-2a). It is more preferable, and it is especially preferable that it is 0.3-15 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

As said photoinitiator in adhesive composition (I-2), the thing similar to the photoinitiator in adhesive composition (I-1) is mentioned.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using a photopolymerization initiator, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 to 20 parts by mass, and preferably 0.03 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is more preferable that it is negative, and it is particularly preferable that it is 0.05 to 5 parts by mass.

[Other additives, solvents]

The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

In addition, the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).

Examples of the other additives and solvents in the PSA composition (I-2) include the same ones as those in the PSA composition (I-1).

The other additives and solvents contained in the pressure-sensitive adhesive composition (I-2) may be used individually or in combination of two or more, and in the case of two or more, their combination and ratio may be arbitrarily selected.

Contents of the other additives and the solvent in the PSA composition (I-2) are not particularly limited, respectively, and may be appropriately selected according to the type.

<Adhesive composition (I-3)>

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

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

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy ray-polymerizable unsaturated group and can be cured by energy ray irradiation, and the pressure-sensitive adhesive composition (I-1) contains The same thing as the energy ray-curable compound to be mentioned.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, and more preferably 0.03 to 200 parts by mass, based on 100 parts by mass of the adhesive resin (I-2a). It is preferable, and it is especially preferable that it is 0.05-100 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. Even if the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

As said photoinitiator in adhesive composition (I-3), the thing similar to the photoinitiator in adhesive composition (I-1) is mentioned.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray curable compound. It is preferable, that it is 0.03-10 mass parts is more preferable, and it is especially preferable that it is 0.05-5 mass parts.

[Other additives, solvents]

The pressure-sensitive adhesive composition (I-3) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

In addition, the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).

Examples of the other additives and solvents in the PSA composition (I-3) include the same ones as the other additives and solvents in PSA composition (I-1), respectively.

The other additives and solvents contained in the pressure-sensitive adhesive composition (I-3) may be used individually or in combination of two or more, and in the case of two or more, their combination and ratio may be arbitrarily selected.

Contents of the other additives and the solvent in the PSA composition (I-3) are not particularly limited, respectively, and may be appropriately selected according to the type.

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

Up to this point, the PSA composition (I-1), PSA composition (I-2), and PSA composition (I-3) have been mainly explained, but what has been described as components containing these is the overall It can be used similarly also in the adhesive composition (in this specification, it is called "adhesive composition other than adhesive composition (I-1) - (I-3)").

As an adhesive composition other than adhesive composition (I-1) - (I-3), a non-energy ray-curable adhesive composition other than an energy ray-curable adhesive composition is also mentioned.

Examples of the non-energy ray-curable adhesive composition include, for example, non-energy ray-curable adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ether, polycarbonate, and ester-based resins (I A pressure-sensitive adhesive composition (I-4) containing -1a) is exemplified, and the one containing an acrylic resin is preferable.

PSA compositions other than PSA compositions (I-1) to (I-3) preferably contain one or more crosslinking agents, the content of which is the same as in the above-mentioned PSA composition (I-1) or the like. can do.

<Adhesive composition (I-4)>

Preferable examples of the pressure-sensitive adhesive composition (I-4) include those containing the above-mentioned pressure-sensitive adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)]

As adhesive resin (I-1a) in adhesive composition (I-4), the same thing as adhesive resin (I-1a) in adhesive composition (I-1) is mentioned.

The adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

[Crosslinking agent]

As the adhesive resin (I-1a), in the case of using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from a (meth)acrylic acid alkyl ester, the adhesive composition (I-4) is further It is preferable to contain a crosslinking agent.

Examples of the crosslinking agent in the PSA composition (I-4) include the same ones as the crosslinking agent in the PSA composition (I-1).

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the PSA 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 0.1 to 25 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -10 mass parts.

[Other additives, solvents]

The pressure-sensitive adhesive composition (I-4) may contain other additives that do not correspond to any of the components described above within a range that does not impair the effects of the present invention.

In addition, the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).

Examples of the other additives and solvents in the PSA composition (I-4) include the same ones as the other additives and solvents in PSA composition (I-1), respectively.

The other additives and solvents contained in the pressure-sensitive adhesive composition (I-4) may be used individually or in combination of two or more, and in the case of two or more, their combination and ratio may be arbitrarily selected.

Contents of the other additives and the solvent in the PSA composition (I-4) are not particularly limited, respectively, and may be appropriately selected according to the type.

<<Manufacturing method of adhesive composition>>

Pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-4) and other pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive (I-1) to (I-3), if necessary It is obtained by mix|blending each component for constituting the adhesive composition, such as components other than the said adhesive.

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

In the case of using a solvent, the solvent may be used by mixing the solvent with any combination component other than the solvent and diluting this combination component in advance, or mixing the solvent with these combination components without diluting any combination component other than the solvent in advance. You may use by mixing.

The method of mixing each component at the time of blending is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade or the like; mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as the method of mixing by applying ultrasonic waves.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

○ Intermediate layer, composition for forming an intermediate layer

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

The intermediate layer may contain only non-silicon resin (made of non-silicon resin), or may contain non-silicon resin and other components.

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

In the middle layer, the ratio of the total content of one or more of the below-mentioned components in the middle layer to the total mass of the middle layer does not exceed 100% by mass.

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

Coating of the composition for forming an intermediate layer can be performed in the same manner as in the case of coating of the above-described pressure-sensitive adhesive composition.

Drying conditions of the composition for forming an intermediate layer are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferable to dry it by heating, and in this case, it is preferable to dry it under conditions of 1 to 6 minutes at 60 to 130°C, for example.

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

In view of further improving the semiconductor wafer splitting ability of the sheet for manufacturing semiconductor devices, the weight average molecular weight of the non-silicon resin may be, for example, 80000 or less, 60000 or less, and 40000 or less.

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

The weight average molecular weight of the non-silicon-based resin can be appropriately adjusted within a range set by arbitrarily combining the aforementioned lower limit and either upper limit. For example, in one embodiment, any one of 5000-100000, 5000-80000, 5000-60000, and 5000-40000 may be sufficient as the said weight average molecular weight, for example.

In the present embodiment, "the middle layer contains a non-silicon-based resin having a weight average molecular weight of 100,000 or less as a main component" means "the middle layer contains a non-silicon-based resin having a weight average molecular weight of 100,000 or less" means that the effect of containing a non-silicon resin having a weight average molecular weight of 100,000 or less can be sufficiently exhibited. contains the non-silicon-based resin in an acceptable amount.” From this point of view, in the intermediate layer, the ratio of the content of the non-silicon-based resin to the total mass of the intermediate layer (in other words, in the composition for forming an intermediate layer, the content of the non-silicon-based resin relative to the total content of all components other than the solvent) The ratio) is preferably 80% by mass or more, more preferably 90% by mass or more, and may be, for example, 95% by mass or more, 97% by mass or more, and 99% by mass or more.

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

The non-silicon-based resin having a weight average molecular weight of 100,000 or less is not particularly limited as long as it is a resin component having a weight average molecular weight of 100,000 or less without having a silicon atom as a constituent atom.

The non-silicon-based resin may be any of a polar resin having a polar group and a non-polar resin having no polar group, for example.

For example, the non-silicon-based resin is preferably a polar resin in terms of high solubility in the composition for forming an intermediate layer and higher coatability of the composition for forming an intermediate layer.

In this specification, "non-silicon-type resin" means a non-silicon-type resin whose above-mentioned weight average molecular weight is 100000 or less unless there is particular notice.

The non-silicon-based resin may be, for example, a homopolymer that is a polymer of one type of monomer (in other words, having only one type of structural unit), or a polymer of two or more types of monomers (in other words, that has two or more types of structural units). ) may be a copolymer.

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

The said polar resin may have only the structural unit which has a polar group, and may have both the structural unit which has a polar group and the structural unit which does not have a polar group.

As a structural unit which has the said polar group, the structural unit derived from vinyl acetate, etc. are mentioned, for example.

As a structural unit which does not have the said polar group, the structural unit derived from ethylene etc. are mentioned, for example.

In the polar resin, the ratio of the mass of the structural units having polar groups to the total mass of all the structural units is preferably 5 to 70% by mass, for example, 7.5 to 55% by mass and 10 to 40% by mass. may be any one of In other words, in the polar resin, the ratio of the mass of structural units without a polar group to the total mass of all the structural units is preferably 30 to 95% by mass, for example, 45 to 92.5% by mass and 60% by mass. Any one of -90 mass % may be sufficient. When the ratio of the mass of constituent units having a polar group is equal to or greater than the lower limit, the polar resin has the characteristic of having a polar group more remarkably. When the ratio of the mass of structural units having a polar group is equal to or less than the above upper limit, the polar resin more appropriately has the characteristics of not having a polar group.

As said polar resin, an ethylene-vinyl acetate copolymer etc. are mentioned, for example.

Among them, the preferred polar resin is, for example, in the ethylene-vinyl acetate copolymer, the ratio of the mass of the structural units derived from vinyl acetate to the total mass of all the structural units (in this specification, "vinyl acetate (sometimes referred to as "the content of structural units derived from") is 10 to 40% by mass. In other words, examples of the above-mentioned preferred polar resins include those in which the ratio of the mass of the constituent units derived from ethylene to the total mass of all the constituent units in the ethylene-vinyl acetate copolymer is 60 to 90% by mass. have.

Examples of the non-polar resin include 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). ) polyethylene (PE) such as; Polypropylene (PP) etc. are mentioned.

The composition for forming an intermediate layer and the non-silicon-based resin contained in the intermediate layer may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.

For example, the composition for forming the intermediate layer and the intermediate layer may contain one or two or more polar resin non-silicon-based resins, and may not contain non-polar non-silicon-based resins. It may contain a species or two or more species, and may not contain a polar resin non-silicon-based resin, and may contain one or two or more species of a polar resin non-silicon-based resin and a non-polar non-silicon-based resin together.

It is preferable that the composition for forming the intermediate layer and the intermediate layer contain at least a non-silicon-based resin which is a polar resin.

In the composition for forming an intermediate layer and the intermediate layer, the ratio of the content of the non-silicon-based resin, which is a polar resin, to the total content of the non-silicon-based resin is preferably 80% by mass or more, and more preferably 90% by mass or more. For example, any one of 95 mass % or more, 97 mass % or more, and 99 mass % or more may be sufficient. When the ratio is equal to or greater than the lower limit, the effect of using the polar resin is obtained more remarkably.

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

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

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

The composition for forming an intermediate layer preferably contains a solvent in addition to the non-silicon resin from the viewpoint of good handleability, and a component that does not correspond to either of the non-silicon resin or the solvent (referred to herein as "additive"). ”) may be contained.

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

Any of a resin component (in this specification, it may be called "other resin component") and a non-resin component may be sufficient as the said additive.

As said other resin component, the weight average molecular weight (Mw) can mention non-silicon-type resin and silicon-type resin more than 100000 (Mw>100000), for example.

A non-silicon resin having a weight average molecular weight of more than 100,000 is not particularly limited as long as it satisfies these conditions.

As will be described later, the intermediate layer containing the silicon-based resin makes it easier to pick up the semiconductor chip on which the film adhesive is formed.

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 silicon-based resin is not particularly limited.

Examples of preferred silicon-based resins include resin components exhibiting a release action with respect to the pressure-sensitive adhesive component, and siloxane-based resins (also known as resin components having a siloxane bond (-Si-O-Si-) and siloxane-based compounds) do) is more preferable.

As said siloxane-type resin, polydialkylsiloxane etc. are mentioned, for example.

It is preferable that the carbon number of the alkyl group of the said polydialkylsiloxane is 1-20.

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

As said polydialkylsiloxane, polydimethylsiloxane etc. are mentioned.

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

The composition for forming an intermediate layer and the above-mentioned additives contained in the intermediate layer may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

For example, the composition for forming an intermediate layer and the intermediate layer may contain one or two or more resin components as the above additives, and may not contain non-resin components, and may contain one or two or more non-resin components. It is contained, and it is not necessary to contain a resin component, and you may contain 1 type(s) or 2 or more types of resin components and non-resin components together.

When the composition for forming an intermediate layer and the intermediate layer contain the above additives, in the intermediate layer, the ratio of the content of the non-silicon-based resin to the total mass of the intermediate layer (that is, in the composition for forming an intermediate layer, the total amount of all components other than the solvent) The ratio of the content of the non-silicon-based resin to the content) is preferably 90 to 99.99% by mass, for example, 90 to 97.5% by mass, 90 to 95% by mass, and 90 to 92.5% by mass. Also, any one of 92.5 to 99.99 mass%, 95 to 99.99 mass%, and 97.5 to 99.99 mass% may be sufficient, and 92.5 to 97.5 mass% may be sufficient.

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

The solvent contained in the composition for forming an intermediate layer is not particularly limited, but is preferably, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-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; and the like.

The solvent contained in the composition for forming an intermediate layer may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The solvent contained in the composition for forming an intermediate layer is preferably tetrahydrofuran or the like from the viewpoint of being able to more uniformly mix the components contained in the composition for forming an intermediate layer.

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

As will be described later, from the point of being able to more easily pick up a semiconductor chip on which a film adhesive is formed, a preferable intermediate layer is, for example, the ethylene-vinyl acetate copolymer as the non-silicon resin and the siloxane-based compound as the additive and the ratio of the content of the ethylene-vinyl acetate copolymer (the non-silicon-based resin) to the total mass of the intermediate layer in the intermediate layer is within any of the above-mentioned numerical ranges, and in the intermediate layer to the total mass of the intermediate layer It is exemplified that the ratio of the content of the siloxane-based compound (the above-mentioned additive) is within any of the numerical ranges described above.

For example, such an intermediate layer contains the ethylene-vinyl acetate copolymer as the non-silicon resin and the siloxane-based compound as the additive, and the content of the ethylene-vinyl acetate copolymer relative to the total mass of the intermediate layer in the intermediate layer is 90 to 99.99% by mass, and the ratio of the content of the siloxane-based compound to the total mass of the middle layer in the middle layer is 0.01 to 10% by mass. However, this is an example of a preferred intermediate layer.

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

In the sheet for semiconductor device manufacture, X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy, In this specification, sometimes referred to as “XPS”), when analysis is performed, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon (in this specification, “the ratio of silicon concentration”) ”) is preferably 1 to 20% on a molar basis of the element. By using the sheet|seat for semiconductor device manufacture provided with such an intermediate|middle layer, as mentioned later, the semiconductor chip on which the film adhesive was formed can be picked up more easily.

In the XPS analysis, the analysis target is the film adhesive side of the intermediate layer, and the X-ray irradiation angle is 45° using an X-ray photoelectron spectroscopy device, the X-ray beam diameter is 20 μmφ, and the output is 4.5 It can be done by setting it to W.

The ratio of the silicon concentration is given by the following formula:

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

can be calculated by

In view of this effect being more remarkable, the ratio of the silicon concentration may be, for example, 4 to 20%, 8 to 20%, and 12 to 20%, or 1 to 16%, on a molar basis of the element. , 1 to 12%, and any one of 1 to 8% may be sufficient, and any one of 4 to 16% and 8 to 12% may be sufficient.

When the XPS analysis is performed as described above, other elements that do not correspond to any of carbon, oxygen, nitrogen, and silicon may be detected on the plane of the intermediate layer (XPS analysis symmetry plane). However, even if the other elements are normally detected, their concentrations are trace amounts, so when calculating the ratio of the silicon concentrations, if the measured values of the concentrations of carbon, oxygen, nitrogen, and silicon are used, the silicon concentration The ratio can be calculated with high precision.

The intermediate layer may consist of one layer (single layer) or may consist of a plurality of layers of two or more layers. don't

As described above, the maximum width of the intermediate layer is preferably smaller than the maximum width of the pressure-sensitive adhesive layer and the maximum width of the base material.

The maximum value of the width of the intermediate layer can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the middle layer may be 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. In these three numerical ranges, the maximum value of the width in the direction parallel to the sticking surface with the sheet for semiconductor device manufacture corresponds to a semiconductor wafer of 150 mm, a semiconductor wafer of 200 mm, or a semiconductor wafer of 300 mm have. However, as described above, in the case of cutting the film adhesive by expanding the sheet for semiconductor device manufacture after performing dicing accompanying formation of the modified layer in the semiconductor wafer, as will be described later, after dicing A plurality of semiconductor chips (semiconductor chip groups) are made into one, and a sheet for manufacturing a semiconductor device is affixed to these semiconductor chips.

In this specification, unless otherwise specified, "the width of the intermediate layer" means, for example, "the width of the intermediate layer in a direction parallel to the first surface of the intermediate layer". For example, in the case of an intermediate layer having a circular planar shape, the maximum width of the intermediate layer described above is the diameter of the circular circular shape.

This is the same for semiconductor wafers. That is, "the width|variety of a semiconductor wafer" means "the width|variety of the semiconductor wafer in the direction parallel with respect to the sticking surface of a semiconductor wafer with the sheet|seat for semiconductor device manufacture." For example, in the case of a semiconductor wafer having a circular planar shape, the maximum width of the semiconductor wafer described above is the diameter of the circular circular planar shape.

The maximum value of the width of the intermediate layer of 150 to 160 mm is equivalent to the maximum value of the width of the semiconductor wafer of 150 mm, or means larger within a range not exceeding 10 mm.

Similarly, the maximum width of the intermediate layer of 200 to 210 mm is equivalent to the maximum width of the semiconductor wafer of 200 mm or larger within a range not exceeding 10 mm.

Similarly, the maximum width of the intermediate layer of 300 to 310 mm is equivalent to the maximum width of the semiconductor wafer of 300 mm or larger within a range not exceeding 10 mm.

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

The thickness of the intermediate layer can be appropriately selected depending on the purpose, but it is preferably 5 to 150 μm, more preferably 5 to 120 μm, and for example, it may be any one of 10 to 90 μm and 10 to 60 μm, Any one of 30-120 micrometers and 60-120 micrometers may be sufficient. When the thickness of the intermediate layer is equal to or greater than the lower limit, the structure of the intermediate layer is further stabilized. When the thickness of an intermediate|middle layer is below the said upper limit, in the case of blade dicing and the said expansion of the sheet|seat for semiconductor device manufacture, a film adhesive can be cut|disconnected more easily.

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

When the intermediate layer contains the silicon-based resin, particularly when the compatibility between the silicon-based resin and the non-silicon-based resin as a main component is low, in the sheet for manufacturing a semiconductor device, the silicon-based resin in the intermediate layer is present on both sides of the intermediate layer (first 1 side and the opposite side) and are likely to be ubiquitous in the area around it. And, the stronger this tendency is, the more easily the film adhesive adjacent to (directly contacting) the intermediate layer peels off from the intermediate layer, and as will be described later, the semiconductor chip on which the film adhesive is formed can be picked up more easily. .

For example, when comparing intermediate layers that differ from each other only in thickness and are identical in terms of composition, area of both sides, etc. (% by mass) are the same as each other. However, the content (part by mass) of the silicon-based resin in the middle layer is greater in the thicker middle layer than in the thin middle layer. Therefore, when the silicon-based resin tends to be unevenly distributed in the intermediate layer as described above, the thicker intermediate layer is more unevenly distributed on both surfaces (the first surface and the opposite side surface) and in the vicinity thereof than in the thin intermediate layer. quantity increases For this reason, even if it does not change the said ratio, it is possible to adjust the pick-up aptitude of the semiconductor chip with film adhesive by adjusting the thickness of the intermediate|middle layer in the sheet|seat for semiconductor device manufacture. For example, the semiconductor chip with film adhesive can be picked up more easily by thickening the thickness of the intermediate|middle layer in the sheet|seat for semiconductor device manufacture.

○Film type adhesive

The film adhesive has curability, preferably has thermosetting properties, and preferably has pressure-sensitive adhesive properties. A film adhesive having both thermosetting and pressure-sensitive adhesive properties can be applied to various adherends by lightly pressing them in an uncured state. Moreover, a film adhesive may be what can be affixed to various to-be-adhered bodies by heating and softening. The film adhesive finally becomes a cured product with high impact resistance by curing, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

When the sheet for semiconductor device manufacture is viewed from above as a plane view, the area of the film adhesive (ie, the area of the first surface) approaches the area of the semiconductor wafer before division, so that the area of the base material (ie, the area of the first surface) area) and the area of the pressure-sensitive adhesive layer (ie, the area of the first surface). In such a sheet for semiconductor device manufacture, a region not in contact with the intermediate layer and the film adhesive (namely, the non-laminated region) exists on a part of the first surface of the pressure-sensitive adhesive layer. While expanding of the sheet for semiconductor device manufacture becomes easier by this, since the force applied to the film adhesive at the time of expansion is not dispersed, the film adhesive can be cut more easily.

A film adhesive can be formed using the adhesive composition containing the constituent material. For example, a film adhesive can be formed in a target site|part by coating an adhesive composition on the formation target surface of a film adhesive and drying it as needed.

Film adhesive WHEREIN: The ratio of the total content of the 1 type, or 2 or more types of below-mentioned component of the film adhesive with respect to the gross mass of the film adhesive does not exceed 100 mass %.

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

Coating of adhesive composition can be performed by the same method as the case of coating of the above-mentioned adhesive composition.

Drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described below, it is preferable to heat dry it, and in this case, it is preferable to dry it under conditions of 10 seconds to 5 minutes at 70 to 130°C, for example.

The film adhesive may consist of one layer (single layer) or may consist of two or more layers, and when it consists of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is particularly Not limited.

As explained above, it is preferable that the maximum value of the width|variety of a film adhesive is made smaller than the maximum value of the width|variety of an adhesive layer, and the maximum value of the width|variety of a base material.

The maximum value of the width of the film adhesive may be the same as the maximum value of the width of the intermediate layer described above with respect to the size of the semiconductor wafer.

That is, the maximum value of the width|variety of a film adhesive can consider the size of a semiconductor wafer, and can select suitably. For example, 150-160 mm, 200-210 mm, or 300-310 mm may be sufficient as the maximum of the width|variety of a film adhesive. These three numerical ranges correspond to semiconductor wafers in which the maximum value of the width in the direction parallel to the bonding surface with the semiconductor device manufacturing sheet is 150 mm semiconductor wafer, 200 mm semiconductor wafer, or 300 mm semiconductor wafer. .

In this specification, "the width|variety of a film adhesive" means "the width|variety of the film adhesive in the direction parallel to the 1st surface of a film adhesive", for example, unless there is particular notice. For example, in the case of a film adhesive having a flat circular shape, the maximum value of the width of the aforementioned film adhesive is the diameter of the flat circular circular shape.

In addition, unless otherwise specified, the "width of the film adhesive" is not the width of the film adhesive after cutting in the manufacturing process of the semiconductor chip with the film adhesive described later, but "before cutting (uncut) The width of the film adhesive" is meant.

The maximum value of the width of the film adhesive of 150-160 mm is equivalent to the maximum value of the width of a semiconductor wafer of 150 mm, or it means a large thing in the range which does not exceed 10 mm.

Similarly, the maximum value of the width of the film adhesive of 200-210 mm is equivalent to the maximum value of the width of a semiconductor wafer of 200 mm, or it means a large thing in the range which does not exceed 10 mm.

Similarly, the maximum value of the width of the film adhesive of 300-310 mm is equal to the maximum value of the width of a semiconductor wafer of 300 mm, or it means a large thing in the range which does not exceed 10 mm.

That is, in this embodiment, the difference between the maximum value of the width of a film adhesive and the maximum value of the width of a semiconductor wafer, for example, the maximum value of the width of a semiconductor wafer is 150 mm, 200 mm, and 300 mm Any of may be 0 to 10 mm.

In this embodiment, any of the numerical ranges mentioned above may be sufficient as both the maximum value of the width|variety of an intermediate|middle layer, and the maximum value of the width|variety of a film adhesive.

That is, in an example of the sheet for semiconductor device manufacture of the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film adhesive are 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. can hear

The thickness of the film 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. When the thickness of the film adhesive is equal to or more than the lower limit, higher adhesive strength is obtained with respect to an adherend (semiconductor chip). When the thickness of the film adhesive is equal to or less than the above upper limit, the film adhesive can be more easily cut at the time of blade dicing and the expansion of the sheet for semiconductor device manufacture.

Here, "the thickness of a film adhesive" means the thickness of the whole film adhesive, and, for example, the thickness of a film adhesive consisting of multiple layers means the total thickness of all the layers which comprise a film adhesive. .

Next, the adhesive composition will be described.

<<adhesive composition>>

Preferred adhesive compositions include, for example, those containing a polymer component (a) and a thermosetting component (b). Hereinafter, each component is demonstrated.

On the other hand, the adhesive composition shown below is a preferable example, and the adhesive composition in this embodiment is not limited to what is shown below.

[Polymer component (a)]

The polymer component (a) is a component that can be considered to have been formed by a polymerization reaction of a polymerizable compound, and imparts film-formability and flexibility to the film adhesive, as well as adhesion to an adhesive object such as a semiconductor chip (in other words, , adhesiveness) is a polymer compound for improving. The polymer component (a) has thermoplasticity and does not have thermosetting properties. In the present specification, the product of polycondensation reaction is also included in the polymer compound.

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

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

Among these, it is preferable that the polymer component (a) is an acrylic resin.

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

[Thermosetting component (b)]

The thermosetting component (b) has thermosetting properties and is a component for thermosetting the film adhesive.

The thermosetting component (b) contained in the adhesive composition and the film adhesive may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

Among these, it is preferable that the thermosetting component (b) is an epoxy-type thermosetting resin.

○Epoxy type thermosetting resin

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

The epoxy-type thermosetting resin contained in the adhesive composition and the film adhesive may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

・Epoxy resin (b1)

Examples of the epoxy resin (b1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolak epoxy resins, and dicyclopenta. Diene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, the reliability of the package obtained using the film adhesive improves by using the epoxy resin which has an unsaturated hydrocarbon group.

The epoxy resin (b1) contained in the adhesive composition and the film adhesive may be one type or two or more types.

・Heat curing agent (b2)

The thermal curing agent (b2) functions as a curing agent for the epoxy resin (b1).

As a thermosetting agent (b2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydride is preferable, and phenol It is more preferable that it is a sexual hydroxyl group or an amino group.

Among the thermosetting agents (b2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. can be heard

Among the thermal curing agents (b2), examples of the amine-based curing agent having an amino group include dicyandiamide (DICY) and the like.

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

The heat curing agent (b2) contained in the adhesive composition and the film adhesive may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the adhesive composition and the film adhesive, the content of the heat curing agent (b2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, based on 100 parts by mass of the epoxy resin (b1). For example, any one of 1-100 mass parts, 1-50 mass parts, and 1-25 mass parts may be sufficient. Hardening of a film adhesive advances more easily because the said content of a thermosetting agent (b2) is more than the said lower limit. When the said content of a thermosetting agent (b2) is below the said upper limit, the moisture absorption rate of a film adhesive reduces and the reliability of the package obtained using a film adhesive improves more.

In the adhesive composition and the film adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is based on 100 parts by mass of the content of the polymer component (a). , 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. . When the content of the thermosetting component (b) is within this range, the peeling force between the intermediate layer and the film adhesive is more stable.

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

Preferred other components contained in the adhesive composition and the film adhesive include, for example, a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray curable resin (g), A photoinitiator (h), general purpose additive (i), etc. are mentioned.

[Curing accelerator (c)]

The curing accelerator (c) is a component for controlling the curing rate of the adhesive composition.

Examples of preferable curing accelerators (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines (phosphine in which one or more hydrogen atoms are substituted with organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate; and the like.

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

When using the curing accelerator (c), in the adhesive composition and the film adhesive, the content of the curing accelerator (c) is preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (b), 0.1 It is more preferable that it is -5 mass parts. When the said content of a hardening accelerator (c) is more than the said lower limit, the effect by using a hardening accelerator (c) is acquired more remarkably. When the content of the curing accelerator (c) is less than or equal to the above upper limit, for example, the highly polar curing accelerator (c) is suppressed from migrating to the adhesion interface side with the adherend and segregating in the film adhesive under high temperature and high humidity conditions. The effect is enhanced and the reliability of the package obtained by using the film adhesive is further improved.

[Filling material (d)]

When the film adhesive contains the filler (d), its cutting properties by expansion are further improved. In addition, by containing the filler (d), the film adhesive becomes easy to adjust the thermal expansion coefficient, and by optimizing this thermal expansion coefficient with respect to the object to which the film adhesive is attached, the reliability of the package obtained by using the film adhesive is higher. It improves. Moreover, when a film adhesive contains a filler (d), the moisture absorption rate of the film adhesive after hardening can be reduced or heat dissipation property can also be improved.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; Beads which spheroidized these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned.

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

The filler (d) contained in the adhesive composition and the film adhesive may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using the filler (d), in the adhesive composition, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, in the film adhesive, for the total mass of the film adhesive The ratio of the content of the filler (d)) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass. When the ratio is within this range, the effect of using the filler (d) is obtained more remarkably.

[Coupling agent (e)]

By containing the coupling agent (e), the film adhesive improves the adhesiveness and adhesiveness to the adherend. Moreover, when a film adhesive contains a coupling agent (e), the hardened|cured material does not impair heat resistance, and water resistance improves. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

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

As for the coupling agent (e) which adhesive composition and a film adhesive contain, only 1 type may be sufficient as it, and 2 or more types may be sufficient as it, and in the case of 2 or more types, these combination and ratio can be arbitrarily selected.

When using the coupling agent (e), in the adhesive composition and the film adhesive, the content of the coupling agent (e) is 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). It is preferable that it is a mass part, it is more preferable that it is 0.05-10 mass parts, and it is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (e) is equal to or greater than the lower limit, the effect of using the coupling agent (e), such as improvement of the dispersibility of the filler (d) in the resin and improvement of the adhesion of the film adhesive to the adherend, etc. is more significantly obtained. Generation|occurrence|production of outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

[Crosslinking agent (f)]

As the polymer component (a), when using a polymer component having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group that can be bonded to other compounds, such as the above-mentioned acrylic resin, an adhesive composition and The film adhesive may contain a crosslinking agent (f). The crosslinking agent (f) is a component for linking the functional group in the polymer component (a) to another compound for crosslinking, and by crosslinking in this way, the initial adhesive force and cohesive force of the film adhesive can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (a crosslinking agent having an aziridinyl group).

When using an organic polyhydric isocyanate compound as a crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as a polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film adhesive by reaction between the crosslinking agent (f) and the polymer component (a).

The crosslinking agent (f) contained in the adhesive composition and the film adhesive may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using a crosslinking agent (f), the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer component (a). It is preferable, and it is especially preferable that it is 0.3-5 mass parts. When the content of the cross-linking agent (f) is equal to or greater than the lower limit, the effect of using the cross-linking agent (f) is obtained more remarkably. Excessive use of the crosslinking agent (f) is suppressed because the said content of the crosslinking agent (f) is below the said upper limit.

[Energy ray curable resin (g)]

Since the adhesive composition and the film adhesive contain the energy ray-curable resin (g), the properties of the film adhesive can be changed by irradiation with energy rays.

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

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

The energy ray-curable resin (g) contained in the adhesive composition may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

[Photoinitiator (h)]

When the adhesive composition and the film adhesive contain the energy ray curable resin (g), they may contain a photopolymerization initiator (h) 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, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin compounds such as benzoindimethyl 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 bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Moreover, as a photoinitiator (h), photosensitizers, such as an amine, etc. are mentioned, for example.

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

In the case of using a photopolymerization initiator (h), the content of the photopolymerization initiator (h) in the adhesive composition is preferably 0.1 to 20 parts by mass, and preferably 1 to 10 parts by mass, based on 100 parts by mass of the energy ray curable resin (g). It is more preferable that it is a mass part, and it is especially preferable that it is 2-5 mass parts.

[Universal additive (i)]

The general-purpose additive (i) may be a known one, and may be arbitrarily selected depending on the purpose, and is not particularly limited, but preferred examples include plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), gettering I can lift my back.

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

Content of adhesive composition and film adhesive is not specifically limited, What is necessary is just to select suitably according to the purpose.

[menstruum]

It is preferable that the adhesive composition further contains a solvent. An adhesive composition containing a solvent has good handleability.

The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-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; and the like.

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

The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint of being able to more uniformly mix the components contained in the adhesive composition.

Content of the solvent of adhesive composition is not specifically limited, What is necessary is just to select suitably according to the kind of components other than a solvent, for example.

<<Method for producing adhesive composition>>

An adhesive composition is obtained by combining each component for constituting it.

The adhesive composition can be prepared by the same method as in the case of the adhesive composition described above, for example, except that the types of ingredients are different.

◇Manufacturing method of sheet for semiconductor device manufacturing

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

For example, the semiconductor device manufacturing sheet may be prepared by preparing a base material, an adhesive layer, an intermediate layer, and a film adhesive in advance, and bonding and laminating them in the order of the base material, the pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive. have.

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

The semiconductor device manufacturing sheet can also be manufactured, for example, by preparing in advance two or more types of intermediate laminates configured by laminating a plurality of layers to constitute the same, and bonding these intermediate laminates to each other. The configuration of the intermediate laminate can be appropriately selected arbitrarily. For example, a first intermediate laminate (corresponding to the support sheet) having a laminated structure of a base material and an adhesive layer, and a second intermediate laminate having a laminated constitution of an intermediate layer and a film adhesive are prepared in advance, The sheet|seat for semiconductor device manufacture can be manufactured by bonding the adhesive layer in a 1st intermediate|middle laminated body and the intermediate|middle layer in a 2nd intermediate|middle laminated body together.

However, this is also an example of the manufacturing method of the sheet|seat for semiconductor device manufacture.

As the above-mentioned sheet for semiconductor device manufacture, both the area of the first surface of the intermediate layer and the area of the first surface of the film adhesive, as shown in FIG. 1 , for example, are the first surface of the pressure-sensitive adhesive layer and the first surface of the base material. When manufacturing a thing smaller than the area of one surface, you may perform by adding the process of processing an intermediate|middle layer and a film adhesive to the target size at any stage in the manufacturing method mentioned above. For example, in the manufacturing method using the second intermediate laminate, a semiconductor device manufacturing sheet is obtained by adding a step of processing the intermediate layer and the film adhesive in the second intermediate laminate to a target size. may be manufactured.

In the case of manufacturing a sheet for semiconductor device manufacture in a state in which a release film is provided on a film adhesive, for example, a film adhesive is prepared on a release film, and the remaining layers are laminated while maintaining this state, A sheet for semiconductor device manufacture may be produced, or a release film may be laminated on the film adhesive after laminating all of the base material, the pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive, and the sheet for semiconductor device manufacture may be produced. What is necessary is just to remove a peeling film at a necessary stage until the use of the sheet|seat for semiconductor device manufacture.

A sheet for semiconductor device manufacture comprising a base material, an adhesive layer, an intermediate layer, a film adhesive, and another layer that does not correspond to any of the release films is obtained by using the above-mentioned manufacturing method at an appropriate timing. It can be manufactured by adding a step of forming and laminating.

An example of a preferable sheet for semiconductor device manufacture of the present embodiment includes a base material, an adhesive layer, an intermediate layer, and a film adhesive,

The pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the base material,

The middle layer contains, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less;

the intermediate layer contains at least a polar resin as the non-silicon resin;

In the middle layer, the ratio of the content of the non-silicon-based resin to the total mass of the middle layer is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; ,

In the middle layer, the ratio of the content of the non-silicon-based resin as the polar resin to the total content of the non-silicon-based resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more. Any one of mass % or more,

In the above polar resin, the ratio of the mass of the structural units having polar groups to the total mass of all the structural units is any one of 5 to 70% by mass, 7.5 to 55% by mass, and 10 to 40% by mass, for producing a semiconductor device. sheets can be lifted.

Another example of the preferred sheet for semiconductor device manufacture of the present embodiment includes a base material, an adhesive layer, an intermediate layer, and a film adhesive,

The pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the base material,

The middle layer contains, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less;

the intermediate layer contains at least a polar resin as the non-silicon resin;

In the middle layer, the ratio of the content of the non-silicon-based resin to the total mass of the middle layer is any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more; ,

In the middle layer, the ratio of the content of the non-silicon-based resin as the polar resin to the total content of the non-silicon-based resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more. Any one of mass % or more,

In the polar resin, the ratio of the mass of the structural units having polar groups to the total mass of all the structural units is any one of 5 to 70% by mass, 7.5 to 55% by mass, and 10 to 40% by mass,

When the surface of the film adhesive side of the intermediate layer was analyzed by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon was 1 to 20% and 4 to 4%, respectively. 16%, and the sheet|seat for semiconductor device manufacture which becomes any of 8 to 12% is mentioned.

Another example of the preferred sheet for semiconductor device manufacture of the present embodiment includes a base material, an adhesive layer, an intermediate layer, and a film adhesive,

The pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the base material,

The middle layer contains, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less, and further contains a silicon-based resin;

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

In the middle layer, the ratio of the content of the non-silicon-based resin to the total mass of the middle layer is 90 to 99.99% by mass, 90 to 97.5% by mass, 90 to 95% by mass, and 90 to 92.5% by mass;

In the middle layer, the ratio of the content of the silicon-based resin to the total mass of the middle layer is any one of 0.01 to 10% by mass, 2.5 to 10% by mass, 5 to 10% by mass, and 7.5 to 10% by mass,

However, in the intermediate layer, the ratio of the total content of the non-silicon-based resin and the silicon-based resin to the total mass of the intermediate layer does not exceed 100% by mass,

In the middle layer, the ratio of the content of the non-silicon-based resin as the polar resin to the total content of the non-silicon-based resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more. Any one of mass % or more,

In the above polar resin, the ratio of the mass of the structural units having polar groups to the total mass of all the structural units is any one of 5 to 70% by mass, 7.5 to 55% by mass, and 10 to 40% by mass, for producing a semiconductor device. sheets can be lifted.

Another example of the preferred sheet for semiconductor device manufacture of the present embodiment includes a base material, an adhesive layer, an intermediate layer, and a film adhesive,

The pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the base material,

The middle layer contains, as a main component, a non-silicon-based resin having a weight average molecular weight of 100,000 or less, and further contains a silicon-based resin;

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

In the middle layer, the ratio of the content of the non-silicon-based resin to the total mass of the middle layer is 90 to 99.99% by mass, 90 to 97.5% by mass, 90 to 95% by mass, and 90 to 92.5% by mass;

In the middle layer, the ratio of the content of the silicon-based resin to the total mass of the middle layer is any one of 0.01 to 10% by mass, 2.5 to 10% by mass, 5 to 10% by mass, and 7.5 to 10% by mass,

However, in the intermediate layer, the ratio of the total content of the non-silicon-based resin and the silicon-based resin to the total mass of the intermediate layer does not exceed 100% by mass,

In the middle layer, the ratio of the content of the non-silicon-based resin as the polar resin to the total content of the non-silicon-based resin is 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more. Any one of mass % or more,

In the polar resin, the ratio of the mass of the structural units having polar groups to the total mass of all the structural units is any one of 5 to 70% by mass, 7.5 to 55% by mass, and 10 to 40% by mass,

and a sheet for manufacturing a semiconductor device in which the thickness of the intermediate layer is any one of 5 to 150 μm, 5 to 120 μm, 30 to 120 μm, and 60 to 120 μm.

◇How to use the sheet for semiconductor device manufacturing (manufacturing method of semiconductor chip with film adhesive)

In the manufacturing process of the semiconductor device, the said sheet|seat for manufacturing a semiconductor device can be used at the time of manufacturing the semiconductor chip on which the film adhesive was formed.

Hereinafter, the usage method of the said sheet|seat for semiconductor device manufacture (the manufacturing method of the semiconductor chip with film adhesive) is demonstrated in detail, referring drawings.

3A, 3B, and 3C are cross-sectional views for schematically explaining an example of a method of using a semiconductor device manufacturing sheet, showing a case in which the semiconductor device manufacturing sheet is attached to a semiconductor wafer and then used. In this method, the sheet for semiconductor device manufacture is used as a dicing die bonding sheet. Here, taking the sheet 101 for semiconductor device manufacture shown in FIG. 1 as an example, the usage method is demonstrated.

First, as shown in FIG. 3A, heating the sheet|seat 101 for semiconductor device manufacture in the state which removed the peeling film 15, the film adhesive 14 in it is heated, and the back surface 9b' of the semiconductor wafer 9' ) attached to

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

Although the heating temperature at the time of sticking of the sheet|seat 101 for semiconductor device manufacture is not specifically limited, It is preferable that it is 40-70 degreeC from the point which the heating sticking stability of the sheet|seat 101 for semiconductor device manufacture improves more.

The maximum value of the width (W ₁₃ ) of the intermediate layer 13 in the sheet 101 for semiconductor device manufacture and the maximum value of the width (W ₁₄ ) of the film adhesive 14 are both the width of the semiconductor wafer 9' ( It is completely equal to or not equal to the maximum value of W _9' ), but the error is slight, and it is almost equal.

For example, when the maximum value of the width W _9' of the semiconductor wafer 9' is 150 mm, the maximum value of the width W ₁₃ of the intermediate layer 13 and the width of the film adhesive 14 The maximum value of (W ₁₄ ) is preferably 150 to 160 mm, and when the maximum value of the width (W ₉ ) of the semiconductor wafer 9′ is 200 mm, the width (W 13 ) of the intermediate layer ₁₃ ), and the maximum value of the width (W ₁₄ ) of the film adhesive 14 is preferably 200 to 210 mm, and the maximum value of the width (W ₉ ) of the semiconductor wafer 9' is 300 In the case of mm, it is preferable that the maximum value of the width (W ₁₃ ) of the intermediate layer 13 and the maximum value of the width (W ₁₄ ) of the film adhesive 14 are 300 to 310 mm.

Thus, in this embodiment, the difference between the maximum value of the width (W ₁₃ ) of the intermediate layer 13 and the maximum value of the width (W _{9 ′} ) of the semiconductor wafer 9', and the film adhesive 14 The difference between the maximum value of the width (W ₁₄ ) and the maximum value of the width (W _{9 ′} ) of the semiconductor wafer 9' may be 0 to 10 mm.

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

Next, the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9' obtained above is cut with a blade from the circuit formation surface 9a' side of the semiconductor wafer 9' (blade dicing). By doing), the film adhesive 14 is cut while dividing the semiconductor wafer 9'.

Blade dicing can be performed by a known method. For example, in the first surface 12a of the pressure-sensitive adhesive layer 12 in the sheet 101 for semiconductor device manufacture, the region in the vicinity of the periphery where the intermediate layer 13 and the film adhesive 14 are not laminated (the non-laminated region) After fixing ) to a jig (not shown) such as a ring frame, the division of the semiconductor wafer 9' and the cutting of the film adhesive 14 can be performed using a blade.

By this process, as shown in FIG. 3B, the semiconductor chip 914 in which the several film adhesive provided with the semiconductor chip 9 and the film adhesive 140 after cutting formed on the back surface 9b was formed is obtained The semiconductor chips 914 formed with these film adhesives are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, constituting the group of semiconductor chips 910 formed with the film adhesives.

The back surface 9b of the semiconductor chip 9 corresponds to the back surface 9b' of the semiconductor wafer 9'. In Fig. 3B, reference numeral 9a indicates the circuit formation surface of the semiconductor chip 9, and corresponds to the circuit formation surface 9a' of the semiconductor wafer 9'.

At the time of blade dicing, while dividing by cutting the entire area|region of the thickness direction about the semiconductor wafer 9' with a blade, about the sheet|seat 101 for semiconductor device manufacture, of the film adhesive 14 It is preferable not to cut the film adhesive 14 in the whole area|region of the thickness direction by cutting from the 1st surface 14a to the area|region in the middle of the intermediate|middle layer 13, and also not cut to the adhesive layer 12. .

That is, at the time of blade dicing, the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9' is cut with a blade in the lamination direction of the circuit formation surface 9a' of the semiconductor wafer 9'. ) to at least the first surface 13a of the intermediate layer 13, and to the surface opposite to the first surface 13a of the intermediate layer 13 (that is, the contact surface with the pressure-sensitive adhesive layer 12). It is preferable not to cut in.

In this step, it is possible to easily avoid that the blade reaches the substrate 11 in this way, and thereby, generation of cutting chips from the substrate 11 can be suppressed. Further, the main component of the middle layer 13 cut by the blade is a non-silicon-based resin having a weight average molecular weight of 100,000 or less, particularly, a weight average molecular weight of 100,000 or less, so that the generation of cutting chips from the middle layer 13 is also suppressed. can do.

The conditions of blade dicing may be appropriately adjusted according to the purpose, and are not particularly limited.

Usually, the rotation speed of the blade is preferably 15000 to 50000 rpm, and the moving speed of the blade is preferably 5 to 75 mm/sec.

After blade dicing, as shown to FIG. 3C, the semiconductor chip 914 with film adhesive is separated from the intermediate|middle layer 13 in the laminated sheet 10, and is picked up. Here, the case where the semiconductor chip 914 on which the film adhesive is formed is separated in the direction of the arrow P is shown using a separating means 7 such as a vacuum collet. On the other hand, the separating means 7 is not cross-sectioned here.

The semiconductor chip 914 on which the film adhesive is formed can be picked up by a known method.

In the 1st surface 13a of the intermediate|middle layer 13, when the ratio of the said silicon concentration is 1 to 20 %, the semiconductor chip 914 with film adhesive can be picked up more easily.

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

In the manufacturing method of the semiconductor chip with the film adhesive described so far, in a preferred embodiment, for example, a semiconductor chip with a film adhesive provided with a semiconductor chip and a film adhesive formed on the back surface of the semiconductor chip As a manufacturing method of

The sheet for manufacturing a semiconductor device includes the base material, an adhesive layer, an intermediate layer, and a film adhesive,

The said manufacturing method is the step of sticking the said film adhesive in it to the back surface of the said semiconductor wafer, heating the said sheet|seat for semiconductor device manufacture, and the said semiconductor wafer to which the said film adhesive was stuck, from the circuit formation surface side , By cutting and dividing the entire region in the thickness direction, the semiconductor chip is produced, and the semiconductor device manufacturing sheet is divided in the thickness direction from the film adhesive side to the region in the middle of the intermediate layer. A step of obtaining a group of semiconductor chips formed with a film adhesive in which a plurality of semiconductor chips formed with the film adhesive are aligned on the intermediate layer by cutting the film adhesive and not cutting to the pressure-sensitive adhesive layer by cutting; , What has the process of isolate|separating and picking up the semiconductor chip with the said film adhesive from the said intermediate|middle layer (in this specification, it may call "the manufacturing method 1") is mentioned.

4A, 4B, and 4C are cross-sectional views for schematically explaining an example of a method for manufacturing a semiconductor chip, which is an object of use of a sheet for manufacturing a semiconductor device, in which dicing accompanying formation of a modified layer is performed in a semiconductor wafer. By doing so, it shows about the case of manufacturing a semiconductor chip.

5A, 5B, and 5C are cross-sectional views for schematically explaining another example of a method of using a semiconductor device manufacturing sheet, showing a case in which the semiconductor device manufacturing sheet is used after being attached to a semiconductor chip. In this method, a sheet for semiconductor device manufacture is used as a die bonding sheet. Here, taking the sheet 101 for semiconductor device manufacture shown in FIG. 1 as an example, the usage method is demonstrated.

First, prior to use of the sheet 101 for semiconductor device manufacture, as shown in Fig. 4A, a semiconductor wafer 9' is prepared, and a back grind tape ("surface protection tape") is applied to the circuit formation surface 9a'. Also referred to as) (8) is attached.

In FIG. 4A, symbol W _9' represents the width of the semiconductor wafer 9'.

Next, by irradiating a laser beam (not shown) so as to focus on a focal point set inside the semiconductor wafer 9', a modified layer 90' is formed inside the semiconductor wafer 9', as shown in FIG. 4B. do.

It is preferable to irradiate the semiconductor wafer 9' with the laser beam from the back surface 9b' side of the semiconductor wafer 9'.

The position of the focal point at this time is the expected division (dicing) position of the semiconductor wafer 9', and is set such that semiconductor chips of a target size, shape, and number can be obtained from the semiconductor wafer 9'.

Next, the back surface 9b' of the semiconductor wafer 9' is ground using a grinder (not shown). As a result, the thickness of the semiconductor wafer 9' is adjusted to a target value, and the modified layer 90' is formed by using the force applied to the semiconductor wafer 9' at the time of grinding. In the part, the semiconductor wafer 9' is divided, and as shown in FIG. 4C, a plurality of semiconductor chips 9 are produced.

Unlike other portions of the semiconductor wafer 9', the modified layer 90' of the semiconductor wafer 9' is altered by laser light irradiation, and the strength is weakened. For this reason, by applying force to the semiconductor wafer 9' on which the modified layer 90' is formed, the force is applied to the modified layer 90', and the semiconductor wafer 9' is formed at the portion of the modified layer 90'. ) is divided, and a plurality of semiconductor chips 9 are obtained.

By the above, the semiconductor chip 9 which is the use object of the sheet|seat 101 for semiconductor device manufacture is obtained. More specifically, by this process, a semiconductor chip group 901 in a state where a plurality of semiconductor chips 9 are arranged and fixed on the back grind tape 8 is obtained.

When the semiconductor chip group 901 is viewed from above as a plan view, a planar shape formed by connecting the outermost parts of the semiconductor chip group 901 (in this specification, such a planar shape is simply referred to as “planar shape of the semiconductor chip group”). ) is completely identical to the planar shape when the semiconductor wafer 9' is viewed from the same plane, or the difference between these planar shapes is negligibly minor, and the semiconductor chip group 901 It can be said that the planar shape of is substantially the same as the planar shape of the semiconductor wafer 9'.

Accordingly, the width of the planar shape of the semiconductor chip group 901 can be regarded as equal to the width W _9' of the semiconductor wafer 9', as shown in FIG. 4C. Also, the maximum value of the width of the planar shape of the semiconductor chip group 901 can be regarded as the same as the maximum value of the width W _9' of the semiconductor wafer 9'.

On the other hand, here, although the case where the semiconductor chip 9 can be produced from the semiconductor wafer 9' as intended is shown, depending on the conditions at the time of grinding the back surface 9b' of the semiconductor wafer 9', In some regions of the semiconductor wafer 9', division into semiconductor chips 9 may not be performed.

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

First, as shown in FIG. 5A, heating the sheet|seat 101 for semiconductor device manufacture of 1 sheet in the state from which the peeling film 15 was removed, the film adhesive 14 in it is all the semiconductor chips in the semiconductor chip group 901. It is affixed to the back surface 9b of (9). The sticking object of the film adhesive 14 at this time may be the semiconductor wafer which is not completely divided|segmented.

The maximum value of the width (W ₁₃ ) of the intermediate layer 13 in the sheet 101 for semiconductor device manufacture and the maximum value of the width (W ₁₄ ) of the film adhesive 14 are both the width of the semiconductor wafer 9' ( W _{9 ′} (that is, the width of the semiconductor chip group 901 ) is completely equal to or not equal to the maximum value, but the error is slight and is almost equal to the maximum value.

That is, the relationship between the maximum value of the width (W ₁₃ ) of the intermediate layer 13 and the maximum value of the width of the semiconductor chip group 901 is the maximum value of the width (W ₁₃ ) of the intermediate layer 13 described above and the semiconductor wafer It may be the same as the relationship of the maximum value of the width W _9' of (9'). And the relationship between the maximum value of the width (W ₁₄ ) of the film adhesive 14 and the maximum value of the width of the semiconductor chip group 901 is the maximum value of the width (W ₁₄ ) of the film adhesive 14 described above. and the maximum value of the width W _9' of the semiconductor wafer 9'.

The sticking of the film adhesive 14 (sheet 101 for semiconductor device manufacture) to the semiconductor chip group 901 at this time, except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9 ', It can carry out by the method similar to the case of sticking of the film adhesive 14 (sheet|seat 101 for semiconductor device manufacture) with respect to the semiconductor wafer 9' in the said manufacturing method 1.

Next, the back grind tape 8 is removed from the semiconductor chip group 901 in a fixed state. And, as shown in FIG. 5B, by extending|stretching in the direction parallel to the surface (for example, the 1st surface 12a of the adhesive layer 12), cooling the sheet|seat 101 for semiconductor device manufacture, fand it Here, the direction of the expand _of the sheet|seat 101 for semiconductor device manufacture is shown by arrow E1. By expanding in this way, the film adhesive 14 is cut|disconnected along the outer periphery of the semiconductor chip 9.

By this process, the semiconductor chip 914 with the several film adhesive provided with the semiconductor chip 9 and the film adhesive 140 after cutting formed in the back surface 9b is obtained. The semiconductor chips 914 formed with these film adhesives are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, constituting the group of semiconductor chips 910 formed with the film adhesives.

Both the semiconductor chip 914 with film adhesive and the semiconductor chip group 910 with film adhesive obtained here are the semiconductor chip 914 with film adhesive obtained in the manufacturing method 1 described above and the group of semiconductor chips with film adhesive. It is substantially the same as the semiconductor chip group 910 .

As described above, when the semiconductor wafer 9' is divided, in the case where the division into semiconductor chips 9 is not performed in a partial region of the semiconductor wafer 9', this region is formed by performing this step. Divided into semiconductor chips.

It is preferable to expand the sheet|seat 101 for semiconductor device manufacture by setting the temperature to -5-5 degreeC. By cooling the sheet|seat 101 for semiconductor device manufacture in this way and expanding (cool expanding), the film adhesive 14 can be cut more easily and with high precision.

The expansion of the sheet|seat 101 for semiconductor device manufacture can be performed by a well-known method. For example, in the first surface 12a of the pressure-sensitive adhesive layer 12 in the sheet 101 for semiconductor device manufacture, the region in the vicinity of the periphery where the intermediate layer 13 and the film adhesive 14 are not laminated (the non-laminated region) After fixing ) to a jig (not shown) such as a ring frame, the entire region where the intermediate layer 13 and the film adhesive 14 of the sheet 101 for semiconductor device manufacture are laminated is separated from the base material 11 by the pressure-sensitive adhesive layer ( 12), the sheet|seat 101 for semiconductor device manufacture can be expanded by pushing up from the base material 11 side.

In FIG. 5B , the non-laminated region in which the intermediate layer 13 and the film adhesive 14 are not laminated among the first surface 12a of the pressure-sensitive adhesive layer 12 is the first surface 13a of the intermediate layer 13 However, as described above, in a state in which the sheet 101 for semiconductor device manufacturing is expanded by pushing up, the non-laminated region approaches the outer circumference of the pressure-sensitive adhesive layer 12, It includes an inclined surface that descends in height in the opposite direction to the direction of push-up.

In this process, since the sheet|seat 101 for semiconductor device manufacture is provided with the intermediate|middle layer 13 (in other words, the film adhesive 14 before cutting is formed on the intermediate|middle layer 13), the film adhesive 14 ) is precisely cut at the target location (in other words, along the outer periphery of the semiconductor chip 9), and cutting defects can be suppressed.

After expansion, as shown to FIG. 5C, the semiconductor chip 914 with film adhesive is separated from the intermediate|middle layer 13 in the laminated sheet 10, and is picked up.

The pick-up at this time can be performed by the same method as the pick-up in the manufacturing method 1 described above, and the pick-up aptitude is also the same as the pick-up aptitude in the manufacturing method 1.

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

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

In the manufacturing method of the semiconductor chip with the film adhesive described so far, in a preferred embodiment, for example, a semiconductor chip with a film adhesive provided with a semiconductor chip and a film adhesive formed on the back surface of the semiconductor chip As a manufacturing method of

The sheet for manufacturing a semiconductor device includes the base material, an adhesive layer, an intermediate layer, and a film adhesive,

The manufacturing method includes a step of forming a modified layer inside a semiconductor wafer by irradiating laser light so as to focus on a focal point set inside the semiconductor wafer, and grinding the back surface of the semiconductor wafer after forming the modified layer. In addition, a step of dividing the semiconductor wafer at a formation site of the modified layer by using a force applied to the semiconductor wafer during grinding to obtain a semiconductor chip group in which a plurality of the semiconductor chips are aligned; While heating the said semiconductor device manufacturing sheet|seat, the process of sticking the said film adhesive in it on the back surface of all the said semiconductor chips in the said semiconductor chip group, cooling the said semiconductor device manufacturing sheet after sticking to the said semiconductor chip, that By stretching in a direction parallel to the surface, the film adhesive is cut along the outer periphery of the semiconductor chip, and a semiconductor chip group on which a plurality of the film adhesive is formed is aligned on the intermediate layer. A step of obtaining and a step of separating and picking up the semiconductor chip on which the film adhesive was formed from the intermediate layer (in this specification, it may be referred to as "manufacturing method 2").

So far, in both cases of Manufacturing Method 1 and Manufacturing Method 2, the sheet 101 for manufacturing a semiconductor device shown in FIG. 1 has been taken as an example and the method of use thereof has been described. also can be used in the same way. In this case, based on the difference in structure between this sheet for semiconductor device manufacture and the sheet 101 for semiconductor device manufacture, other steps may be appropriately added to use the semiconductor device manufacture sheet, if necessary.

Not limited to the case of Manufacturing Method 1 and Manufacturing Method 2, after obtaining the semiconductor chip group on which the film adhesive is formed, before picking up the semiconductor chip on which the film adhesive is formed, the laminated sheet is placed as the intermediate layer of the pressure-sensitive adhesive layer. Expanded in a direction parallel to the side surface (first surface), and further maintaining this state, the semiconductor chip with the film adhesive (semiconductor chip group with the film adhesive) is mounted in the laminated sheet. You may heat the peripheral part which has not been made.

By doing in this way, the distance between adjacent semiconductor chips, that is, the kerf width, can be kept sufficiently wide and highly uniform on the laminated sheet while shrinking the periphery. And the semiconductor chip on which the film adhesive was formed can be picked up more easily.

Example

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

<<Manufacturing Raw Material of Adhesive Composition>>

The raw material used for manufacture of adhesive composition is shown below.

[Polymer component (a)]

(a)-1: An acrylic resin obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass) (weight average molecular weight: 800,000, glass transition temperature: 9°C).

[Epoxy resin (b1)]

(b1)-1: Cresol novolak-type epoxy resin to which an acryloyl group was added ("CNA147" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518 g/eq, number average molecular weight 2100, unsaturated group content equal to epoxy group).

[Heat curing agent (b2)]

(b2)-1: aralkyl type phenolic resin (Mirex XLC-4L manufactured by Mitsui Chemicals, number average molecular weight: 1100, softening point: 63°C)

[Filling material (d)]

(d)-1: Spherical silica (“YA050C-MJE” manufactured by Admatechs, average particle diameter 50 nm, methacrylsilane treated product)

[Coupling agent (e)]

(e)-1: Silane coupling agent, 3-glycidoxypropylmethyldiethoxysilane ("KBE-402" manufactured by Shin-Etsu Silicone Co., Ltd.)

[Crosslinking agent (f)]

(f)-1: tolylene diisocyanate-based crosslinking agent ("Coronate L" manufactured by Tosoh Corporation)

[Example 1]

<<Manufacture of Sheet for Manufacturing Semiconductor Devices>>

<Manufacture of base material>

Using an extruder, low-density polyethylene (LDPE, Sumitomo Chemical Co., Ltd. "Sumikasen L705") is melted, the melt is extruded by the T-die method, and the extrudate is biaxially stretched using a cooling roll, thereby making LDPE. A substrate (thickness 110 μm) was obtained.

<Production of pressure-sensitive adhesive layer>

Specific energy ray curing properties containing an acrylic resin ("Oribine BPS 6367X" manufactured by Toyochem) (100 parts by mass) and a crosslinking agent ("BXX 5640" manufactured by Toyochem Corporation) (1 part by mass) as the adhesive resin (I-1a) An adhesive composition was prepared.

Next, using a release film in which one side of the polyethylene terephthalate film has been subjected to a release treatment by silicone treatment, the adhesive composition obtained above is applied to the release treatment side, and the specific energy is heated and dried at 100° C. for 2 minutes. A precurable pressure-sensitive adhesive layer (thickness of 10 μm) was produced.

＜Production of the middle layer＞

At room temperature, an ethylene-vinyl acetate copolymer (EVA, weight average molecular weight: 30000, content of structural units derived from vinyl acetate: 25% by mass) (15 g) was dissolved in 85 g of tetrahydrofuran, and a siloxane-based compound (polydimethyl Siloxane, "BYK-333" manufactured by Big Chemie Japan Co., Ltd., the number of structural units represented by the formula "-Si(-CH ₃ ) ₂ -O-" in 1 molecule (45 to 230) (1.5 g) was added and stirred. By doing so, a composition for forming an intermediate layer was produced.

An intermediate layer ( thickness 20 μm) was produced.

<Production of film adhesive>

Polymer component (a)-1 (100 parts by mass), epoxy resin (b1)-1 (10 parts by mass), heat curing agent (b2)-1 (1.5 parts by mass), filler (d)-1 (75 parts by mass) , coupling agent (e)-1 (0.5 parts by mass), and crosslinking agent (f)-1 (0.5 parts by mass) were prepared.

Next, using a release film in which one side of the film made of polyethylene terephthalate has been subjected to a release treatment by silicone treatment, the adhesive composition obtained above is applied to the release treatment side, and the adhesive composition obtained above is applied and heat-dried at 80° C. for 2 minutes to form a thermosetting film. A mold adhesive (thickness 7 μm) was prepared.

<Production of Sheet for Manufacturing Semiconductor Devices>

The first intermediate laminate with a release film (in other words, the support with the release film formed) by bonding the exposed surface on the opposite side of the side provided with the release film of the pressure-sensitive adhesive layer obtained above to one surface of the base material obtained above. sheet) was created.

2nd in which the release film was formed by bonding the exposed surface of the film adhesive obtained above, on the side opposite to the side provided with the release film, to the exposed surface on the opposite side to the side provided with the release film of the intermediate layer obtained above. An intermediate laminate (a laminate of a release film, an intermediate layer, a film adhesive, and a release film) was produced.

Then, with respect to the second intermediate laminate in which the release film was formed, a punching process is performed using a cutting blade from the release film on the intermediate layer side to the film adhesive, and unnecessary portions are removed, thereby forming a layer on the release film on the side of the film adhesive. Then, a film adhesive (thickness of 7 μm) having a circular plane shape (diameter of 305 mm), an intermediate layer (thickness of 20 μm), and a release film were laminated in this order in their thickness direction, and a release film was formed. A second intermediate laminate workpiece was produced.

Next, the peeling film was removed from the 1st intermediate|middle laminated body with the peeling film obtained above, and one side of the adhesive layer was exposed.

Further, from the second intermediate laminate workpiece with a release film obtained above, the circular release film was removed to expose one side of the intermediate layer.

Next, the newly formed exposed surface of the pressure-sensitive adhesive layer in the first intermediate laminate and the newly formed exposed surface of the intermediate layer in the processed product of the second intermediate laminate were bonded together. With respect to the base material and the pressure-sensitive adhesive layer (namely, support sheet) in the laminate thus obtained, the planar shape of these (support sheet) is circular (diameter 370 mm), and furthermore, the circular film adhesive and the intermediate layer (diameter 305 mm) ) and concentric, punching was performed from the substrate side using a cutting blade (diameter: 370 mm) to remove unnecessary portions.

As described above, the base material (thickness: 110 μm), the pressure-sensitive adhesive layer (thickness: 10 μm), the intermediate layer (thickness: 20 μm), the film adhesive (thickness: 7 μm), and the release film are laminated in this order in their thickness direction. Thus, a sheet for manufacturing a semiconductor device having a release film formed thereon was obtained.

<<Evaluation of Sheet for Manufacturing Semiconductor Devices>>

<Calculation of the ratio of the silicon concentration in the surface of the film adhesive side of the intermediate layer>

In the manufacturing process of the above-mentioned semiconductor device manufacturing sheet, the exposed surface of the intermediate layer in the step before bonding with the pressure-sensitive adhesive layer was analyzed by XPS, and carbon (C), oxygen (O), nitrogen (N), and The concentration (atomic %) of silicon (Si) was measured, and the ratio (%) of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon was determined from the measured value.

The XPS analysis was performed using an X-ray photoelectron spectroscopy apparatus (“Quantra SXM” manufactured by Albac Co., Ltd.) under the conditions of an irradiation angle of 45°, an X-ray beam diameter of 20 µmφ, and an output of 4.5 W. The results are shown in the "Concentration ratio of elements in the middle layer (%)" column in Table 1 together with the ratio (%) of the concentrations of other elements.

<Evaluation of the effect of suppressing the generation of cutting chips during blade dicing>

[Production of Silicon Chip Group with Film Adhesive]

In the sheet for semiconductor device manufacture obtained above, the release film was removed.

A silicon wafer (diameter: 300 mm, thickness: 75 μm) whose back surface is polished with a dry polish finish is used, and a tape mounter ("Adwill RAD2500" manufactured by Lintech) is used on the back surface (polished surface) to manufacture the above semiconductor device. The sheet was affixed with the film adhesive while heating at 60°C. Thus, a laminate composed of a base material, an adhesive layer, an intermediate layer, a film adhesive, and a silicon wafer being laminated in this order in their thickness direction (the laminated sheet, the film adhesive, and the silicon wafer in this order) , a laminate structured by being laminated in their thickness direction) was obtained.

Next, of the first surface of the pressure-sensitive adhesive layer in the laminate, a region in the vicinity of the periphery where no intermediate layer was formed (the non-laminated region) was fixed to a ring frame for wafer dicing.

Next, while dividing|segmenting a silicon wafer by dicing using a dicing apparatus ("DFD6361" by a Disco company), the film adhesive was also cut, and the size obtained the silicon chip of 8 mm x 8 mm. In the dicing at this time, the rotational speed of the blade is 30000 rpm and the moving speed of the blade is 30 mm/sec, and the film adhesive is applied to the sheet for semiconductor device production from the surface of the silicon wafer to the intermediate layer area. (That is, from the entire area of the film adhesive in the thickness direction and from the surface on the film adhesive side of the intermediate layer to the area in the middle) It performed by cutting with a blade. As a blade, "Z05-SD2000-D1-90 CC" manufactured by Disco was used.

As a result of the above, the silicon chip and the silicon chip formed with a large number of film adhesives having a film adhesive formed on the back surface after cutting are aligned and fixed on the intermediate layer in the laminated sheet by the film adhesive therein. , a silicon chip group on which a film adhesive was formed was obtained.

[Evaluation of the effect of suppressing the generation of cutting chips]

Using a digital microscope (“VH-Z100” manufactured by Keyence Corporation), the silicon chip group with the film adhesive obtained above was observed from above on the silicon chip side, and the presence or absence of cutting chips was confirmed. And when no cutting chips were generated, it was determined as "A", and when cutting chips were generated even slightly, it was determined as "B". The results are shown in Table 1.

<Evaluation of cutability of film adhesive at the time of expansion>

[Production of Silicon Chip Group with Film Adhesive]

A silicon wafer having a circular planar shape, a diameter of 300 mm, and a thickness of 775 µm was used, and a back grind tape ("Adwill E-3100TN" manufactured by Lintec) was attached to one side thereof.

Subsequently, a modified layer was formed inside the silicon wafer by irradiating a laser beam so as to focus on a focal point set inside the silicon wafer using a laser beam irradiation device ("DFL73161" manufactured by Disco). At this time, the focus was set such that a large number of silicon chips having a size of 8 mm x 8 mm were obtained from the silicon wafer. In addition, the laser beam was irradiated from the other surface (surface to which the back grind tape was not applied) to the silicon wafer.

Next, by grinding the other surface of the silicon wafer using a grinder, the thickness of the silicon wafer is set to 30 μm, and the force applied to the silicon wafer at this time is used to form a modified layer At the site, a silicon wafer was divided to produce a plurality of silicon chips. As a result, a silicon chip group in a state where a plurality of silicon chips were aligned and fixed on the back grind tape was obtained.

Next, using a tape mounter (“Adwill RAD2500” manufactured by Lintec Corporation), while heating the obtained sheet for semiconductor device manufacturing at 60° C., the film adhesive in it is applied to all of the silicon chips (silicon chip group) to the other silicon chips (group of silicon chips). It was affixed to the side (that is, the grinding side).

Next, of the first surface of the pressure-sensitive adhesive layer in the sheet for semiconductor device manufacture after being attached to this silicon chip group, the region near the periphery where no intermediate layer was formed (the non-laminated region) was fixed to a ring frame for wafer dicing.

Next, the back grind tape was removed from this group of silicon chips in a fixed state. Then, using a fully automatic die separator (“DDS2300” manufactured by Disco), the sheet for semiconductor device manufacturing is expanded in a direction parallel to the surface while cooling the sheet for semiconductor device manufacturing in an environment of 0° C. Cut along the outer circumference. At this time, the periphery of the sheet for semiconductor device manufacture was fixed, and the entire region in which the intermediate layer and the film adhesive of the sheet for semiconductor device manufacture were laminated was pushed up by a height of 15 mm from the substrate side to expand.

As a result, a film adhesive in which a silicon chip and a plurality of film adhesives having a silicon chip and a film adhesive after cutting formed on the other surface (grinding surface) thereof are formed are aligned and fixed on the intermediate layer. A group of formed silicon chips was obtained.

Next, after canceling the expansion of the above-described sheet for semiconductor device manufacture once, a laminate composed of a base material, an adhesive layer, and an intermediate layer (i.e., the laminated sheet) being laminated at room temperature with respect to the first surface of the pressure-sensitive adhesive layer. Expanded in a parallel direction. Further, while maintaining this expanded state, the periphery on which the silicon chip on which the film adhesive was formed was not mounted was heated among the laminated sheets. As a result, the kerf width between adjacent silicon chips was maintained at a constant value or more on the laminated sheet while shrinking the peripheral portion.

[Evaluation of cutability of film adhesive]

In the production of the silicon chip group with the film adhesive described above, the silicon chip group with the film adhesive obtained above was observed from above the silicon chip side using a digital microscope (“VH-Z100” manufactured by Keyence Corporation). . Then, by the expansion of the semiconductor device manufacturing sheet, the film adhesive is formed when it is assumed that the film adhesive is normally cut, and the cutting line of a plurality of film adhesives extending in one direction and extending in a direction orthogonal to this direction Among the cutting lines of a plurality of film adhesives, the number of cutting lines not actually formed and cutting lines with incomplete formation was confirmed, and the cutting property of the film adhesive was evaluated according to the following evaluation criteria. The results are shown in Table 1.

(Evaluation standard)

A: The total number of pieces of the cutting line of the film adhesive which is not actually formed and the cutting line of the film adhesive in which formation is incomplete is 5 or less.

B: The total number of the cutting lines of the film adhesive which is not actually formed and the cutting line of the film adhesive in which formation is incomplete is 6 or more.

<Evaluation of pickup properties of silicon chips with film adhesive after expansion>

After evaluating the cutability of the above-described film adhesive, successively, using a silicon chip group on which the film adhesive was formed and a die bonding device (“PU100” manufactured by Fasford Technology Co., Ltd.), a lifting height of 250 μm and a lifting speed of 5 On conditions of mm/s and a pushing-up time of 500 ms, the silicon chip with the film adhesive was picked up from the intermediate layer in the laminated sheet. And when all the silicon chips with film adhesive were able to be picked up normally, it was evaluated as "A", and when the silicon chip with one or more film adhesives could not be picked up normally, it was evaluated as "B". The results are shown in Table 1.

<Measurement of T-shaped peel strength between the intermediate layer and the film adhesive>

In the sheet for semiconductor device manufacture obtained above, the release film was removed.

Laminate obtained by bonding the entire surface of the exposed surface of the film adhesive in the sheet for semiconductor device manufacture thus formed to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer (“PET50(A) PL new 8LK” manufactured by Lintec). A test piece was produced by cutting water into a size of 50 mm x 100 mm.

In this test piece, in accordance with JIS K6854-3, the laminate of the base material, the pressure-sensitive adhesive layer, and the intermediate layer (namely, the laminated sheet), the laminate of the film adhesive and the adhesive tape is peeled off to make the test piece T-shaped. was peeled off, and the maximum value of the peel force (mN/50 mm) measured at this time was employed as the T-shaped peel strength. At this time, the peeling speed was 50 mm/min. The results are shown in Table 1.

<<Production and Evaluation of Sheet for Manufacturing Semiconductor Devices>>

[Example 2]

A sheet for semiconductor device manufacture was prepared and evaluated in the same manner as in Example 1, except that the coating amount of the composition for forming an intermediate layer was increased and the thickness of the intermediate layer was changed to 80 μm instead of 20 μm. The results are shown in Table 1.

[Example 3]

In preparing the composition for forming an intermediate layer, the siloxane-based compound was not added, and the amount of the ethylene-vinyl acetate copolymer was 16.5 g instead of 15 g (in other words, the siloxane-based compound was mixed with the same mass of the ethylene-vinyl acetate copolymer). A sheet for semiconductor device manufacture was prepared and evaluated in the same manner as in Example 1, except that the mixture was substituted with a polymer and only the ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran. The results are shown in Table 1. Description of "-" in the column of additives in Table 1 means that this additive is not used.

[Comparative Example 1]

In preparing the composition for forming the intermediate layer, an ethylene-vinyl acetate copolymer (EVA, weight average molecular weight: 200,000, content of structural units derived from vinyl acetate: 25% by mass) of the same mass was used instead of the above ethylene-vinyl acetate copolymer, and A sheet for semiconductor device manufacture was prepared and evaluated in the same manner as in Example 1, except that the coating amount of the composition for forming an intermediate layer was increased and the thickness of the intermediate layer was changed to 80 μm instead of 20 μm. The results are shown in Table 1.

[Comparative Example 2]

In the preparation of the composition for forming the intermediate layer, an ethylene-vinyl acetate copolymer (EVA, weight average molecular weight: 200000, content of structural units derived from vinyl acetate: 25% by mass) of the same mass was used instead of the above-mentioned ethylene-vinyl acetate copolymer, except that , In the same manner as in the case of Example 1, a sheet for semiconductor device manufacture was manufactured and evaluated. The results are shown in Table 1.

As is evident from the above results, in Examples 1 to 3, the generation of cutting chips is suppressed during blade dicing, and the cutting defect of the film adhesive is suppressed during expansion, resulting in semiconductor wafer division aptitude. this was 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 semiconductor device manufacture was 30000.

On the other hand, in Examples 1 to 3, in the middle layer, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the middle layer is 90.9% by mass or more, and the siloxane-based compound with respect to the total mass of the middle layer The ratio of content was 9.1 mass % or less.

Moreover, in Examples 1-2, the pick-up property of the silicon chip with the film adhesive after expansion was excellent further.

In Examples 1 and 2, the T-shaped peel strength between the intermediate layer and the film adhesive was appropriately low, such as 100 mN/50 mm or less, and the ratio of the silicon concentration in the intermediate layer was appropriately high, such as 9%. . These evaluation results matched the evaluation results of pick-up properties of the silicon chip with the film adhesive.

In Example 3, the intermediate layer in the sheet for semiconductor device manufacture did not contain the siloxane-based compound.

The difference between the semiconductor device manufacturing sheets of Examples 1 and 2 is only the thickness of the intermediate layer, but the T-shaped peel strength between the intermediate layer and the film adhesive is higher in the semiconductor device manufacturing sheet of Example 2 than in the semiconductor device manufacturing sheet of Example 1. Small, Example 2 was easier to pick up the silicon chip on which the film adhesive was formed than Example 1. This means that even if the ratio (mass%) of the content of the siloxane-based compound to the total mass of the intermediate layer in the intermediate layer is the same as that of the semiconductor device manufacturing sheet of Examples 1 and 2, the content (part by mass) of the siloxane-based compound in the intermediate layer is Example 2 is larger than Example 1, and furthermore, in the middle layer, since the siloxane-based compound tends to be unevenly distributed on both sides of the middle layer and in the vicinity thereof, It was estimated that the amount of Example 2 was greater than that of Example 1.

On the other hand, in Examples 1 to 3, nitrogen was not detected upon XPS analysis of the exposed surface of the intermediate layer.

On the other hand, in Comparative Examples 1 and 2, generation of cutting chips was not suppressed during blade dicing, and the splitting ability of the semiconductor wafer was poor.

In Comparative Examples 1 and 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 semiconductor device manufacture was 200,000.

On the other hand, the difference between the semiconductor device manufacturing sheets of Comparative Examples 1 and 2 is only the thickness of the intermediate layer, and the relationship between the T-shaped peel strength between the intermediate layer and the film adhesive in Comparative Examples 1 and 2 is that of Examples 1 and 2. showed the same trend as in the case of

Also in Comparative Examples 1 and 2, nitrogen was not detected in the XPS analysis of the exposed surface of the intermediate layer.

The present invention can be used for manufacturing semiconductor devices.

101... sheet for semiconductor device manufacture, 11 . . . description, 12 . . . pressure-sensitive adhesive layer, 13 . . . middle layer, 13a... 1st side of the middle layer, 14 . . . film adhesive

Claims (3)

A base material, an adhesive layer, an intermediate layer, and a film adhesive,
The pressure-sensitive adhesive layer, the intermediate layer, and the film adhesive are laminated in this order on the base material,
The sheet|seat for semiconductor device manufacture in which the said intermediate|middle layer contains as a main component the non-silicon-type resin whose weight average molecular weight is 100000 or less. According to claim 1,
When the surface of the film adhesive side of the intermediate layer 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%, Sheets for manufacturing semiconductor devices. According to claim 1 or 2,
The intermediate layer contains the ethylene-vinyl acetate copolymer, which is the non-silicon resin, and a siloxane-based compound;
In the ethylene-vinyl acetate copolymer, the ratio of the mass of the structural units derived from vinyl acetate to the total mass of all the structural units is 10 to 40% by mass,
In the middle layer, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the middle layer is 90 to 99.99% by mass,
In the intermediate layer, the ratio of the content of the siloxane-based compound to the total mass of the intermediate layer is from 0.01 to 10% by mass.

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