TW201900803A - Film adhesive composite sheet and method of manufacturing semiconductor device - Google Patents

Abstract

A film-type adhesive composite sheet which includes a curable film-type adhesive provided on a support sheet, wherein the support sheet includes a substrate, a thickness of the curable film-type adhesive is 1 to 60 [mu]m, and the product of the Young's modulus of the support sheet and the thickness of the support sheet is 4 to 150 Mpa.mm.

Description

   Film-shaped adhesive compound sheet and method for manufacturing semiconductor device   

The present invention relates to a film-shaped adhesive compound sheet and a method for manufacturing a semiconductor device.

This application claims priority based on Japanese Patent Application No. 2017-063654 filed in Japan on March 28, 2017, and the contents of this application are incorporated herein by reference.

In the manufacturing process of a semiconductor device, a semiconductor wafer to which a film-shaped adhesive for die bonding is attached is sometimes used. As a method for obtaining such a semiconductor wafer with a film-shaped adhesive, there is a method of applying a film-shaped adhesive to a plurality of singulated semiconductor wafers obtained by dicing a semiconductor wafer. The film-shaped adhesive is cut at a position corresponding to the arrangement position of the semiconductor wafer. In this method, a film-shaped adhesive composite sheet provided with a film-shaped adhesive on a support sheet is generally used, and the film-shaped adhesive is attached to a plurality of semiconductor wafers. The semiconductor wafer is produced, for example, by forming a groove on the semiconductor wafer and polishing the back side until the groove reaches the groove. However, this method is an example, and the semiconductor wafer may be produced by other methods. The semiconductor wafer to which the cut-off film-shaped adhesive is attached is separated (picked) from the support sheet together with the film-shaped adhesive, and is used for die bonding.

Among the methods described above, as a method of cutting the film-shaped adhesive, for example, a method of cutting the film-shaped adhesive by irradiating a laser or a method of cutting the film-shaped adhesive by expanding is known. However, the method of irradiating a laser has a problem that a laser irradiating device is required and cannot be cut off in a short time and efficiently. In addition, the method of performing expansion has problems that an expansion device is required and the cut surface is sometimes rough. Furthermore, in the case of expansion, the force acts only in the same direction as the film-shaped adhesive, so it is possible that the film-shaped adhesive extends only with the support sheet without being cut. Therefore, the film-shaped adhesive may be cooled and the film-shaped adhesive may be easily cut and expanded, but in this case, a cooling step is required, and productivity is poor.

As a method to solve these problems, the following method has been disclosed: using a film-shaped adhesive with a specific thickness and tensile elongation at break, in a stage immediately before picking up a semiconductor wafer, the semiconductor wafer together with the uncut film The sheet-shaped adhesive is lifted in the pickup direction together, and the film-shaped adhesive is cut by the shearing force generated at this time (see Patent Document 1).

[Prior technical literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2013-179317.

However, in the method disclosed in Patent Document 1, it is uncertain whether it is possible to pick up a semiconductor wafer to which a film-shaped adhesive after the cutting is attached from a support sheet while suppressing the occurrence of a step abnormality.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a film-shaped adhesive composite sheet provided with a film-shaped adhesive on a support sheet and a method for manufacturing a semiconductor device using the composite sheet. When manufacturing a semiconductor device, a simplified method is used to suppress the occurrence of abnormal steps, and the semiconductor wafer to which the film-shaped adhesive is attached is separated from the support sheet.

In order to solve the above-mentioned problems, the present invention provides a film-like adhesive composite sheet, which is provided on a supporting sheet having a substrate with a hardening film-like adhesive having a thickness of 1 μm to 60 μm. The Young's modulus of the supporting sheet The product (A × B) of A (MPa) and the thickness B (mm) of the aforementioned support sheet is at 4 MPa. mm to 150MPa. The range of mm.

In the film-shaped adhesive composite sheet of the present invention, it is preferable that the elongation at break C of the laminate obtained by laminating the film-shaped adhesive before curing to a total thickness of 200 m is 5% to 2000%.

In addition, the present invention provides a method for manufacturing a semiconductor device using the film-shaped adhesive composite sheet, and further comprising attaching the film-shaped adhesive composite sheet to a plurality of divided semiconductor wafers through the film-shaped adhesive. Step: For the support sheet of the film-shaped adhesive composite sheet attached to the semiconductor wafer, apply force from the side opposite to the side where the film-shaped adhesive is provided, thereby bonding the film through the support sheet. A step of cutting the film-shaped adhesive with a force applied to the film; and a step of separating the film-shaped adhesive from the semiconductor wafer and the film-shaped adhesive adhered to the semiconductor wafer from the support sheet.

That is, the present invention includes the following aspects.

[1] A film-shaped adhesive compound sheet, which is provided on a support sheet with a hardening film-shaped adhesive, and the support sheet has a base material, the thickness of the hardening film-shaped adhesive is 1 μm to 60 μm, and the support sheet is The product of the Young's coefficient and the thickness of the aforementioned support sheet is 4 MPa. mm to 150MPa. mm.

[2] The film-shaped adhesive compound sheet according to [1], wherein the film-shaped adhesive has the following characteristics: when the film-shaped adhesive before curing is laminated to form a laminate having a total thickness of 200 μm; The breaking elongation of the aforementioned laminated body is 1% to 2000%.

[3] A method for manufacturing a semiconductor device, comprising using the film-like adhesive composite sheet according to [1], and including attaching the film-like adhesive composite sheet to a divided sheet via the film-like adhesive. A plurality of semiconductor wafers; with respect to the support sheet in the film-shaped adhesive composite sheet attached to the semiconductor wafer, the film is interposed from the side opposite to the side on which the film-shaped adhesive is provided via the support sheet. A force is applied to the film-shaped adhesive to cut the film-shaped adhesive; and the semiconductor wafer and the film-shaped adhesive after the cutting is attached to the semiconductor wafer are separated from the support sheet.

According to the present invention, there is provided a film-shaped adhesive composite sheet provided with a film-shaped adhesive on a support sheet and a method for manufacturing a semiconductor device using the composite sheet. The simplified method suppresses the occurrence of step abnormalities and separates the semiconductor wafer to which the film-shaped adhesive is attached from the support sheet.

1, 7‧‧‧ film adhesive compound sheet

9‧‧‧ semiconductor wafer

9b‧‧‧ Back of semiconductor wafer

11, 71‧‧‧ support videos

11a‧‧‧ Support surface

11b‧‧‧ Back of support

12, 72‧‧‧ film adhesive

81‧‧‧Top

82‧‧‧lifting department

121‧‧‧ first zone

122‧‧‧Second Zone

811‧‧‧ raised

812‧‧‧ slider

812a‧‧‧Surface of slider

FIG. 1 is a cross-sectional view schematically showing an embodiment from the cutting of a film-like adhesive to the separation of a semiconductor wafer from a support sheet in a method of manufacturing a semiconductor device according to the present invention.

2 is a cross-sectional view schematically illustrating another embodiment of a method for manufacturing a semiconductor device according to the present invention, in which a film-shaped adhesive is urged and the film-shaped adhesive is cut.

FIG. 3 is a cross-sectional view schematically showing one aspect of a film-shaped adhesive composite sheet and a semiconductor wafer in a manufacturing process of a semiconductor device when a conventional film-shaped adhesive composite sheet is used.

FIG. 4 is a cross-sectional view schematically showing another aspect of the film-shaped adhesive composite sheet and the semiconductor wafer during the manufacturing process of the semiconductor device when a conventional film-shaped adhesive composite sheet is used.

<< Film Adhesive Composite Sheet >>

The film-shaped adhesive composite sheet of the present invention is a film-shaped adhesive having a thickness of 1 μm to 60 μm provided on a supporting sheet having a substrate. The Young's coefficient (A) (MPa) of the supporting sheet and the The product of thickness (B) (mm) (that is, the value of A × B) is at 4 MPa. mm to 150MPa. The range of mm.

The film-shaped adhesive composite sheet is provided with a film-shaped adhesive on a support sheet, and is attached to one surface of a semiconductor wafer by the film-shaped adhesive when a semiconductor device is manufactured. In a subsequent step, the semiconductor wafer is separated (picked) from the support sheet while the film-shaped adhesive is attached.

At this time, in the film-shaped adhesive composite sheet, the product (A × B) of the Young's coefficient (A) (MPa) of the support sheet and the thickness (B) (mm) of the support sheet is 4 MPa. mm to 150MPa. The range of mm can suppress the occurrence of step abnormalities and separate the semiconductor wafer to which the film-shaped adhesive is attached from the support sheet.

As one aspect, the product (A × B) of the Young's coefficient (A) (MPa) of the support sheet and the thickness (B) (mm) of the support sheet is preferably 13.6 MPa. mm to 112.5MPa. mm.

More specifically, it is as follows.

First, the film-like adhesive can be cut by performing a normal pick-up operation to apply force to the film-like adhesive through a support sheet. That is, the film-shaped adhesive can be cut at the target portion at room temperature without having to separately provide a step whose main purpose is to cut the film-shaped adhesive. Therefore, it is possible to suppress defective (lifting) of the semiconductor wafer with the film-shaped adhesive not being cut.

In addition, the phenomenon that the portion corresponding to the target semiconductor wafer in the film-shaped adhesive is peeled from the support sheet, and the portion corresponding to the semiconductor wafer outside the target in the film-shaped adhesive is peeled from the support sheet is suppressed. Therefore, it is possible to suppress poor separation (lifting) of the semiconductor wafer caused by the target portion of the film-shaped adhesive not being peeled from the support sheet, or not only the target semiconductor wafer but also the semiconductor wafer adjacent to the target semiconductor wafer and the film-shaped adhesive The generation of so-called double grains that are separated from the support sheet together.

In addition, the "suppression of step abnormality" in this specification refers to the above-mentioned failure of the semiconductor wafer and the suppression of the occurrence of double dies.

It can be considered that if the product (A × B) of the Young's coefficient (A) (MPa) of the aforementioned support sheet and the thickness (B) (mm) of the aforementioned support sheet is less than 4 MPa. mm, the substrate is greatly deformed, and the pickup force is not transmitted to the film-shaped adhesive, and cutting of the film-shaped adhesive becomes difficult. In addition, it can be considered that if the product (A × B) exceeds 150 MPa. mm means that the substrate is hard, and the area around the target film-shaped adhesive corresponding to the semiconductor wafer is also lifted, and the force at the time of pickup is not transmitted to the film-shaped adhesive, and cutting of the film-shaped adhesive becomes difficult.

As one aspect, if the product (A × B) of the Young's coefficient (A) (MPa) of the support sheet and the thickness (B) (mm) of the support sheet is 4 MPa. mm to 150MPa. In the range of mm, the substrate is not greatly deformed, and the pickup force is easily transmitted to the film-shaped adhesive, so cutting of the film-shaped adhesive is easy. In addition, the substrate does not become too hard, and the surrounding area of the target film-shaped adhesive corresponding to the semiconductor wafer can be suppressed from rising. Therefore, the force at the time of picking up is easily transmitted to the film-shaped adhesive. easily.

In this way, by using the aforementioned film-shaped adhesive compound sheet, it is possible to suppress the occurrence of poor separation of the semiconductor wafer and the occurrence of double crystal grains. In addition, the above-mentioned steps, such as cutting the film-shaped adhesive, may be omitted, such as the step of cutting the film-shaped adhesive by irradiating the film, or the step of cutting by expanding the film-shaped adhesive. The problems caused by performing these steps can be avoided, and the film-like adhesive can be cut off at normal temperature, and the number of steps can be reduced, and a simplified method can be used to manufacture a semiconductor device.

In contrast, the above-mentioned "Japanese Patent Application Laid-Open No. 2013-179317" (Patent Document 1) discloses a method of combining a semiconductor wafer with an uncut film-shaped adhesive in a stage immediately before picking up the semiconductor wafer. Lift up in the picking direction, and use the shearing force generated at this time to cut the film adhesive. However, in this method, it is uncertain whether it is possible to suppress the occurrence of step abnormalities and pick up a semiconductor wafer to which a film-shaped adhesive after cutting is attached from a support sheet. For example, it is uncertain whether or not the semiconductor wafer is normally separated from the support sheet in a state of being provided with the film-shaped adhesive after the cutting. The example of this document specifically discloses a film-shaped adhesive composite sheet in which a film-shaped adhesive is provided on a general dicing sheet (that is, a support sheet having a base material and an adhesive layer). The effect is not revealed.

<Support film>

The aforementioned support sheet is a sheet having a base material, which may be a sheet composed of only a base material (that is, only a base material), or a sheet having a base material and layers other than the base material. Examples of the support sheet having another layer include a sheet having an adhesive layer on a substrate.

The film-shaped adhesive agent mentioned later is provided on a support sheet. Therefore, for example, when the support sheet is a sheet having an adhesive layer on a substrate, a film-like adhesive is provided on the adhesive layer. When a support sheet is a sheet | seat comprised only of a base material, a film-shaped adhesive agent is provided in direct contact with the said base material.

The thickness of the support sheet may be appropriately selected depending on the purpose within a range that satisfies the conditions of the aforementioned product (A × B), preferably 20 μm to 200 μm, more preferably 25 μm to 150 μm, particularly preferably 30 μm to 100 μm, and most preferably 38 μm to 80 μm.

Here, the "thickness of the support sheet" refers to the thickness of the entire support sheet. For example, the thickness of the support sheet composed of a plurality of layers refers to the total thickness of all layers constituting the support sheet. In addition, as a method for measuring the thickness of the support sheet, for example, a method of measuring the thickness at any of five positions by a contact thickness meter and calculating an average value of the measured values of the thickness can be cited.

The Young's coefficient of the support sheet can be appropriately selected according to the purpose within a range that fully satisfies the condition of the product (A × B), preferably 50 MPa to 5000 MPa, more preferably 100 MPa to 4000 MPa, and even more preferably 150 MPa to 3000 MPa. It is 170MPa to 2250MPa.

The "Young's coefficient" is measured under the conditions of 100 mm between fixtures and 200 mm / min using a universal testing machine in accordance with JIS (Japanese industrial standard) K7127: 1999 as described in the examples described later. Value.

As one aspect, the supporting sheet of the present invention preferably has a thickness (B) of 38 μm to 80 μm, a Young's coefficient (A) of 170 MPa to 2250 MPa, and a product of these (A × B) of 13.6 MPa. mm to 112.5MPa. mm.

[Substrate]

The constituent material of the substrate is preferably various resins, and specific examples include polyethylene (for example, low density polyethylene (sometimes referred to as LDPE), linear low density polyethylene (sometimes referred to as LLDPE), High-density polyethylene (sometimes referred to as HDPE, etc.)), polypropylene, polybutene, polybutadiene, polymethylpentene, styrene-ethylene butene-styrene block copolymer, polyvinyl chloride, Vinyl chloride copolymer, polyethylene terephthalate (sometimes referred to as PET), polybutylene terephthalate, polyurethane, polyacrylate urethane, polyimide, Ethylene vinyl acetate copolymer, ionic polymer resin, ethylene- (meth) acrylic copolymer, ethylene- (meth) acrylate copolymer, polystyrene, polycarbonate, fluororesin, hydrogenation of any of these resins Materials, modified products, crosslinked products or copolymers.

In addition, in this specification, a "(meth) acryl" means the concept which includes both "acryl" and "methacryl." The terms similar to (meth) acrylic acid are also the same. For example, the so-called "(meth) acrylate" is a concept including both "acrylate" and "methacrylate", and the so-called "(meth) acryl" The concept includes both "acrylfluorenyl" and "methacrylfluorenyl".

The resin constituting the substrate may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

The substrate may be composed of one layer (ie, a single layer), or may be composed of two or more layers. When the substrate is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. That is, all layers may be the same, or all layers may be different, or only some of the layers may be the same. Moreover, when the plural layers are different from each other, the combination of the plural layers is not particularly limited as long as the effect of the present invention is not impaired. Here, the plurality of layers being different from each other means that at least one of a material and a thickness of each layer is different from each other.

Furthermore, in this specification, it is not limited to the case of a base material, so that "a plurality of layers may be the same as or different from each other" means that "all layers may be the same, or all layers may be different, or only a part of the layers may be the same", Furthermore, "the plural layers are different from each other" means "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 according to the purpose within a range that satisfies the conditions of the product (A × B), preferably 20 μm to 200 μm, more preferably 25 μm to 150 μm, even more preferably 30 μm to 100 μm, and most preferably 38 μm Up to 80 μm.

Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. In addition, as a method of measuring the thickness of the base material, for example, a method of measuring the thickness at any five places using a contact thickness meter, and calculating an average value of the measured values.

The Young's coefficient of the substrate can be appropriately selected according to the purpose within a range that fully satisfies the condition of the product (A × B), preferably 50 MPa to 5000 MPa, more preferably 100 MPa to 4000 MPa, and even more preferably 150 MPa to 3000 MPa. It is 170MPa to 2250MPa.

As one aspect, the substrate of the present invention preferably has a thickness of 38 μm to 80 μm, a Young's coefficient of 170 MPa to 2250 MPa, and a product of these is 13.6 MPa. mm to 112.5MPa. mm.

The substrate may also be subjected to the following treatments on the surface in order to improve the adhesion with other layers such as an adhesive layer provided on the substrate: a roughening treatment using a sandblasting treatment, a solvent treatment, or the like; or a corona discharge treatment; Beam irradiation treatment, plasma treatment, ozone treatment, ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments.

In addition, the substrate may be subjected to a primer treatment on the surface.

In addition, the substrate may have an antistatic coating, a layer that prevents the substrate from adhering to another sheet, or a substrate that is adhering to the adsorption table when the film-like adhesive composite sheet is stacked and stored.

Among these, in terms of suppressing the occurrence of chipping of the substrate due to blade friction when dicing the semiconductor wafer, the substrate is particularly preferably subjected to an electron beam irradiation treatment on the surface.

[Adhesive layer]

The said adhesive layer can use a well-known thing suitably.

The adhesive layer may be formed of an adhesive composition containing various components for constituting the adhesive layer. The ratio of the content of the components which are not vaporized at ordinary temperature in the adhesive composition to each other is usually the same as the ratio of the content of the aforementioned components to each other in the adhesive layer. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or particularly hot, that is, ordinary temperature, for example, the temperature of 15 degreeC-25 degreeC, etc. are mentioned.

In a case where the adhesive layer contains an energy ray-curable component, the energy of the energy ray-curable component is reduced by irradiating the energy ray, and the pickup of the semiconductor wafer becomes easier. The treatment of reducing the adhesiveness by irradiating the adhesive layer with energy rays may be performed after the film-like adhesive compound sheet is attached to the adherend, or may be performed in advance before being attached to the adherend.

In the present invention, the "energy line" refers to a person having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of the energy line include ultraviolet rays and electron beams.

The ultraviolet rays can be irradiated, for example, by using a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like as an ultraviolet source. The electron beam can be irradiated by a generator such as an electron beam accelerator.

In the present invention, the "energy ray hardenability" refers to a property that is hardened by irradiating energy rays, and the "non-energy ray hardenability" refers to a property that does not harden even when energy rays are irradiated.

As the adhesive composition, for example, a composition containing an acrylic polymer and an energy ray polymerizable compound (adhesive composition (i)); an acrylic polymer having a hydroxyl group and a polymerizable group in a side chain ( For example, a composition having a hydroxyl group and a polymerizable group in a side chain via a urethane bond) and an isocyanate-based crosslinking agent (adhesive composition (ii)), more preferably a composition further containing a solvent .

In addition to the above components, the adhesive composition may further contain a photopolymerization initiator or a colorant (pigment, dye), an anti-deterioration agent, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent. And any of a variety of additives.

The said adhesive composition may contain the reaction delaying agent which suppresses the progress of an unintended crosslinking reaction during storage. Examples of the reaction delaying agent include those that hinder the function of a component of a catalyst that causes a crosslinking reaction to proceed. Preferred examples include those that form a chelate complex by chelation of the catalyst. As a preferable reaction delaying agent, more specific examples include those having two or more carbonyl groups (-C (= O)-) in the molecule, and those having two carbonyl groups in the molecule include, for example, dicarboxylic acid, keto acid, and dicarboxylic acid. Ketones, etc.

When the support sheet has an adhesive layer, the thickness of the adhesive layer can be appropriately selected according to the purpose within a range that fully satisfies the product (A × B), preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, especially It is preferably 1 μm to 30 μm. The "thickness of the adhesive layer" herein refers to the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer. In addition, as a method for measuring the thickness of the adhesive layer, for example, a method of measuring the thickness at any five places using a contact thickness meter and calculating an average value of the measured values can be cited.

The adhesive composition is obtained by blending the components constituting the adhesive layer, such as an acrylic polymer, and can be obtained, for example, by the same method as in the case of the adhesive composition described later except that the blending components are different.

The adhesive layer can be formed by applying an adhesive composition on the surface of the substrate and drying it.

At this time, if necessary, the applied adhesive composition may be crosslinked by heating. The heating conditions may be, for example, 100 ° C. to 130 ° C. and 1 minute to 5 minutes, but are not limited thereto. In addition, an adhesive layer formed by applying an adhesive composition to the release-treated surface of the release film and drying it is adhered to the surface of the substrate, and if necessary, the aforementioned release film is removed, whereby the substrate can also be applied to the substrate. An adhesive layer is formed thereon.

The application of the adhesive composition to the substrate surface or the release layer surface of the release material may be performed by a known method, and examples thereof include the use of an air knife coater, a blade coater, a bar coater, and a gravure. Coater, roll coater, roll knife coater, curtain coater, die coater, blade coater, screen coater, Meyer bar coater, Methods of various coaters such as anastomotic coaters.

<Film Adhesive>

The film-shaped adhesive is hardenable. The film-shaped adhesive preferably has thermosetting properties, and more preferably has pressure-sensitive adhesive properties. A film-shaped adhesive having both thermosetting and pressure-sensitive adhesive properties can be attached by gently pressing on various adherends in an uncured state. In addition, the film-shaped adhesive can be softened by heating and can be attached to various adherends. The film-shaped adhesive is finally hardened to become a hardened product with high impact resistance, and the hardened product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The thickness of the film adhesive is 1 μm to 60 μm, preferably 3 μm to 25 μm, and more preferably 5 μm to 15 μm. When the thickness of the film-shaped adhesive is greater than or equal to the aforementioned lower limit, a high adhesive force to an adherend (ie, a semiconductor wafer) is obtained. In addition, when the thickness of the film-shaped adhesive is equal to or less than the aforementioned upper limit value, and by performing an operation to apply force to the film-shaped adhesive through a support sheet when a semiconductor device is manufactured, the shear generated in this operation can be used. The cutting force easily cuts the film-shaped adhesive, and there is no need to separately provide a step whose main purpose is to cut the film-shaped adhesive.

As a method for measuring the thickness of the film-shaped adhesive, for example, a method of measuring the thickness at any five places using a contact thickness meter and calculating an average value of the measured values can be cited.

In the present invention, the elongation at break C of the laminate obtained by laminating the aforementioned film-shaped adhesive before curing such that the total thickness becomes 200 μm is, for example, preferably from 5% to 2000%, more preferably from 30% to 1200%, Furthermore, it is preferably 40% to 1100%, and particularly preferably 45% to 1050%. When the elongation at break (C) is equal to or less than the aforementioned upper limit value, the film-shaped adhesive can be more easily cut before picking up the semiconductor wafer to which the film-shaped adhesive is attached.

That is, as one aspect, the film-shaped adhesive in the film-shaped adhesive composite sheet of the present invention has the following characteristics: When the film-shaped adhesive before curing is laminated to form a laminated body having a total thickness of 200 μm, The elongation at break (C) of the aforementioned laminated body is 1% to 2000%, preferably 30% to 1200%, more preferably 40% to 1100%, and even more preferably 45% to 1050%.

As another aspect, the elongation at break (C) is preferably 2000% or less, more preferably 1500% or less, and even more preferably 1000% or less. For example, it may be 30% to 1500%, 40% to 500%, and 45%. Up to 1000%. When the elongation at break (C) is equal to or less than the aforementioned upper limit value, the film-shaped adhesive can be more easily cut in various ways before picking up the semiconductor wafer to which the film-shaped adhesive is attached.

That is, as the cutting method of the film-like adhesive, not only the most common pin-up method, but also other methods such as the slider-up method can be preferably applied. Versatility becomes higher.

In the present specification, the "elongation at break (C) (%)" refers to the elongation at break of a laminate obtained by laminating the aforementioned film-shaped adhesive before curing so that the total thickness becomes 200 μm.

In the present invention, the elongation at break of the film-shaped adhesive before curing or the entire laminate obtained by laminating the film-shaped adhesive before curing is based on JIS K7161-1994 (ISO (International Organization for Standardization; International Standardization Organization)) 527-1) or JIS K7127: 1999 (ISO 527-3). The tensile fracture strain can be measured when the measurement object (test piece) does not have a drop point, and the nominal strain at break can be measured when there is a drop point, and the elongation at break can be determined using these measured values.

The laminated body for which the elongation at break C is to be determined is a film-shaped adhesive before hardening having a thickness of less than 200 μm, and preferably a film having a thickness of 1 μm to 60 μm before constituting the film-shaped adhesive composite sheet of the present invention. A laminated body obtained by laminating two or more film adhesives with a total thickness of 200 μm.

The elongation at break C is obtained by cutting the laminated body into test pieces having a width of 15 mm, a length of 100 mm, and a thickness of 200 μm, and the test pieces are fixed at a distance between parts (for example, by a universal testing machine). The fixing jig fixes the test piece at two places when the distance between the top ends of the aforementioned fixing jigs is 75 mm. Fix it at two places, set the stretching speed to 200 mm / min, and stretch the laminate between the fixed parts. The elongation of the test piece when the laminated body was broken was measured.

In addition, in the present specification, the "elongation at break (C) is X% (where X is a positive number)" means a tensile test piece (a test piece made of a laminate) in the above-mentioned measurement method, When the test piece is stretched by X% of its original length (length when not stretched) in the tensile direction of the test piece, that is, the overall length in the tensile direction of the test piece becomes stretched When the previous length is [1 + X / 100] times, the test piece breaks.

In the present invention, the fracture strength (D) of the laminate obtained by laminating the aforementioned film-shaped adhesive before hardening to a total thickness of 200 μm is preferably 0.1 MPa to 17 MPa, more preferably 0.2 MPa to 15 MPa, and particularly preferably It is 0.4MPa to 13MPa. The so-called laminated system is the same as the laminated body that is the measurement target of the elongation at break (C) (%).

The breaking strength D is the tensile stress when the test piece breaks (is broken) when measuring the elongation at break (C), that is, the tensile breaking stress, and can be measured simultaneously with the elongation at break (C).

That is, as one aspect, the film-shaped adhesive in the film-shaped adhesive composite sheet of the present invention has the following characteristics: When the film-shaped adhesive before curing is laminated to form a laminated body having a total thickness of 200 μm, The breaking strength (D) of the aforementioned laminated body is preferably 0.1 MPa to 17 MPa, more preferably 0.2 MPa to 15 MPa, and even more preferably 0.4 MPa to 13 MPa.

The adhesive force (E) of the film adhesive to the semiconductor wafer before curing is preferably 3N / 24mm or more, and more preferably 4N / 24mm or more. The upper limit of the force (E) can be set to any of 15N / 24mm, 11N / 24mm, and 10N / 24mm, but these are examples. As one aspect, the film-shaped adhesive in the film-shaped adhesive composite sheet of the present invention has the following characteristics: the adhesive force (E) when the film-shaped adhesive before curing is bonded to a semiconductor wafer is preferably 3N Above / 24mm and below 15N / 24mm, more preferably between 3N / 24mm and 11N / 24mm, particularly preferably between 4N / 24mm and 11N / 24mm, and most preferably between 4N / 24mm and 10N / 24mm.

In this specification, the adhesive force E (N / 24mm) of the film adhesive to a semiconductor wafer before curing can be measured by the following method. That is, a laminated sheet with a film-shaped adhesive and an adhesive tape having a width of 24 mm and an arbitrary length was produced. This laminated sheet is formed by laminating a film-shaped adhesive on the adhesive surface of the adhesive tape, and as the adhesive tape is a 24 mm wide adhesive tape of "Cellotape (registered trademark) No. 405" manufactured by Nichiban Corporation. Then, the laminated sheet was attached to a semiconductor wafer by a film-like adhesive heated to 60 ° C., and a laminated body having an adhesive tape, a film-like adhesive, and a semiconductor wafer sequentially laminated was produced. The laminated body was immediately placed in a standard environment specified by JIS Z0237 2009 for 30 minutes, and then the so-called 180 ° peeling was performed, that is, the contact surfaces of the film-shaped adhesive and the semiconductor wafer were 180 ° from each other. The laminated sheet of the film-like adhesive and the adhesive tape was separated from the semiconductor wafer at a peeling speed of 150 mm / min by an angle method. The peel force at this time was measured, and this measured value was made into adhesive force E (N / 24mm). The length of the laminated sheet to be measured is not particularly limited as long as it is a range in which the peel force can be measured stably. The length of the laminated sheet is, for example, preferably 120 mm to 250 mm.

The adhesive force (E) of the film-shaped adhesive to the semiconductor wafer before curing can be adjusted by adjusting the type and amount of the component of the film-shaped adhesive, the thickness of the film-shaped adhesive, and forming the film-like configuration in the support sheet. The material of the surface of the adhesive, the state of the surface (surface state), and the like are appropriately adjusted.

For example, if it is a component of a film-shaped adhesive, by adjusting the type or amount of a coupling agent (e) such as a silane coupling agent described later, the adhesion force of the film-shaped adhesive before curing to a semiconductor wafer can be easily adjusted. E.

In addition, for example, the aforementioned surface state of the support sheet can be adjusted by, for example, implementing the following treatments: the surface treatments listed above as the treatments for improving the adhesion between the substrate and other layers, that is, using sandblasting treatment, solvent treatment, etc Corrugation treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone treatment, ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; primer treatment and so on.

However, these adjustment methods are only examples.

The aforementioned elongation at break (C) and breaking strength (D) of the film-shaped adhesive can be appropriately adjusted by adjusting the kinds and amounts of the components contained in the film-shaped adhesive. For example, it is possible to easily adjust the molecular weight and content of the polymer component (a) described later, the structure, the softening point and content of the components constituting the epoxy-based thermosetting resin (b), and the content of the filler (c). Adjust the elongation at break (C) and the breaking strength (D) of the film adhesive.

However, these adjustment methods are only examples.

In the present invention, the value of E / (C × D) determined based on the elongation at break (C), the breaking strength (D), and the adhesive force (E) is preferably 0.0005 or more, and more preferably 0.0006. Above, particularly preferably, it is 0.0007 or more. The upper limit of E / (C × D) is not particularly limited, and may be any one of 0.80 or less, 0.50 or less, and 0.10 or less, but these are examples.

As one aspect, the film-shaped adhesive in the film-shaped adhesive composite sheet of the present invention has the following characteristics: determined from the elongation at break (C), the strength at break (D), and the adhesion (E). The value of E / (C × D) is preferably 0.0005 or more and 0.80 or less, more preferably 0.0006 or more and 0.50 or less, and even more preferably 0.0007 or more and 0.10 or less.

[Adhesive composition]

The film-shaped adhesive can be formed from an adhesive composition containing the material constituting the film-shaped adhesive. For example, a film-shaped adhesive can be formed on a target part by applying an adhesive composition on the surface to be formed of the film-shaped adhesive and drying it if necessary. The ratio of the content of the components which are not vaporized at ordinary temperature in the adhesive composition is usually the same as the ratio of the content of the aforementioned components in the film-shaped adhesive. Here, the "normal temperature" is as described above.

The application of the 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, and a roll. Knife coater, curtain coater, mold coater, blade coater, screen coater, Meyer bar coater, anastomotic coater and other coaters.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent to be described later, it is preferable to perform drying by heating. In this case, for example, it is preferably 70 ° C to 130 ° C for 10 seconds. Dry to 5 minutes.

As a preferable adhesive composition, the composition containing a polymer component (a) and an epoxy-type thermosetting resin (b) is mentioned, for example. Hereinafter, each component is demonstrated.

(Polymer component (a))

The polymer component (a) is a component which is considered to be formed by a polymerization reaction of a polymerizable compound. The polymer component (a) is used to impart film-forming property, flexibility, and the like to a film-like adhesive, and to adhere to a semiconductor wafer or the like (Adhesiveness) Improved polymer compound. The polymer component (a) is also a component that does not correspond to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The polymer component (a) may be used singly or in combination of two or more kinds. When two or more kinds of polymer components are used in combination, the combination and ratio of these may be arbitrarily selected.

Examples of the polymer component (a) include an acrylic resin (for example, a resin having a (meth) acryl group), a polyester, and a urethane resin (for example, a resin having a urethane bond). ), Acrylic urethane resin, silicone-based resin (for example, resin having a siloxane bond), rubber-based resin (for example, resin having a rubber structure), phenoxy resin, thermosetting polyimide, etc. Is preferably an acrylic resin.

Examples of the acrylic resin in the polymer component (a) include known acrylic polymers.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is within such a range, it is easy to adjust the adhesion force E of the film-like adhesive before curing to the semiconductor wafer within the above range.

On the other hand, when the weight average molecular weight of the acrylic resin is at least the aforementioned lower limit value, the shape stability (stability over time during storage) of the film-shaped adhesive is improved. In addition, since the weight average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit value, the film-shaped adhesive easily follows the uneven surface of the adherend, and the generation of voids and the like between the adherend and the film-shaped adhesive is further suppressed.

In addition, the "weight average molecular weight" in this specification is a polystyrene conversion value measured by the gel permeation chromatography (sometimes abbreviated to GPC) method unless there is particular notice.

The glass transition temperature (sometimes simply referred to as Tg) of the acrylic resin is preferably -60 ° C to 70 ° C, and more preferably -30 ° C to 50 ° C. Since the Tg of the acrylic resin is equal to or more than the aforementioned lower limit value, the adhesion force between the film-shaped adhesive and the support sheet is suppressed, and it becomes easier to separate the semiconductor wafer with the film-shaped adhesive from the support sheet when picking up. In addition, when the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit value, the adhesion E between the film-shaped adhesive and the semiconductor wafer is increased.

Examples of the (meth) acrylate constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (formyl) (Hexyl) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n- (meth) acrylate Nonyl ester, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also known as (meth) acrylic acid Lauryl), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also known as myristyl (meth) acrylate), pentadecyl (meth) acrylate, Hexadecyl (meth) acrylate (also known as palmityl (meth) acrylate), Heptadecyl (meth) acrylate, Stearyl (meth) acrylate (also known as (methyl) Base) stearyl acrylate) Alkyl (meth) acrylic acid alkyl esters having a chain structure of 1 to 18 carbons; Esters, cycloalkyl (meth) acrylates such as dicyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; dicyclopentenyl (meth) acrylate Cycloalkenyl (meth) acrylate, etc .; Cycloalkenyl (meth) acrylate, etc., such as dicyclopentenyloxyethyl (meth) acrylate; (meth) acrylamidoimine; (Glycidyl) glycidyl acrylate-containing (meth) acrylates; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ) Acrylate; N-methylaminoethyl (meth) acrylate and the like (meth) acrylate containing a substituted amine group. Here, the "substituted amino group" refers to a group in which one or two hydrogen atoms of an amine group are substituted with a group other than a hydrogen atom.

The acrylic resin may be selected from, for example, (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methyl methacrylamide, in addition to the (meth) acrylate. Copolymerization of one or two or more monomers.

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

The acrylic resin may have a functional group such as a vinyl group, a (meth) acrylfluorenyl group, an amine group, a hydroxyl group, a carboxyl group, or an isocyanate group, which can be bonded to another compound. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (f) described later, or may be directly bonded to another compound without passing through the cross-linking agent (f). The acrylic resin uses the aforementioned functional group to bond with other compounds, and thus the reliability of the package obtained by using the film-like adhesive compound sheet tends to be improved.

In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter sometimes referred to simply as a "thermoplastic resin") may be used alone without using an acrylic resin, or a thermoplastic resin and an acrylic resin may be used. Use resin together. By using the aforementioned thermoplastic resin, it is sometimes easier to separate a semiconductor wafer provided with a film-like adhesive from a support sheet when picking up, and the film-like adhesive easily follows the uneven surface of the adherend, and adheres to the adherend and the film. Formation of voids and the like between the adhesives is further suppressed.

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

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

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

The thermoplastic resin contained in the adhesive composition and the film-shaped adhesive may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition, the content of the acrylic resin in the polymer component (a) with respect to the total content (total mass) of all components except the solvent (that is, the acrylic resin in the polymer component (a) with respect to The content of the total mass of the film-shaped adhesive is preferably 5 to 40% by mass, and more preferably 7 to 25% by mass.

In the adhesive composition, the content of the polymer component (a) with respect to the total content (mass) of all components other than the solvent (that is, the content of the polymer component (a) with respect to the total mass of the film-shaped adhesive) does not Depending on the kind of the polymer component (a), it is preferably 5 to 85 mass%, and more preferably 7 to 80 mass%.

By using the aforementioned thermoplastic resin, the above-mentioned effects can be obtained, but on the other hand, when the film-shaped adhesive before curing is exposed to a high temperature, the hardness of the film-shaped adhesive is reduced, and the film is not hardened or semi-hardened. In the state of the film-like adhesive, the wire bonding suitability is reduced. Therefore, the content of the polymer component (a) in the adhesive composition is preferably set in consideration of such effects.

(Epoxy-based thermosetting resin (b))

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

The epoxy-based thermosetting resin (b) contained in the adhesive composition and the film-shaped adhesive may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.

． Epoxy resin (b1)

Known examples of the epoxy resin (b1) include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrides thereof, o-cresol novolac epoxy resin, and Difunctional epoxy compounds such as cyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and phenylene skeleton epoxy resin.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of epoxy groups of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth) acrylic acid or a derivative thereof to an addition reaction with an epoxy group. The term "derivative" in this specification means a compound in which at least one group of the original compound is substituted with another group (substituent group) unless otherwise specified. The so-called "base" here refers not only to a group of atoms bonded by a plurality of atoms, but also to one atom.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (ethenyl) (also known as vinyl) and 2-propenyl (also known as allyl). Group), (meth) acrylfluorenyl group, (meth) acrylfluorenylamino group, etc., and preferably acrylfluorenyl group.

The weight average molecular weight of the epoxy resin (b1) is not particularly limited, and it is preferably from 300 to 30,000 in terms of the curability of the film-like adhesive and the strength and heat resistance of the film-like adhesive after curing.

The epoxy equivalent of the epoxy resin (b1) is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 800 g / eq.

In the present specification, the "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured in accordance with the method of JIS K 7236: 2001.

The epoxy resin (b1) may be used singly or in combination of two or more kinds. When two or more kinds of epoxy resins are used in combination, the combination and ratio of these may be arbitrarily selected.

． Heat hardener (b2)

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

Examples of the thermosetting agent (b2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid group obtained by anhydriding, and the phenolic hydroxyl group, an amine group, or an acid group is preferably anhydrided. The group is more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (b2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and biphenyl-type phenols. Resin, aralkyl-type phenol resin, etc.

Among the thermal curing agents (B2), examples of the amine-based curing agent having an amine group include dicyandiamine (hereinafter sometimes referred to simply as "DICY").

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

Examples of the thermosetting agent (b2) having an unsaturated hydrocarbon group include compounds in which a part of hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of the phenol resin. And other compounds.

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

When a phenol-based hardener is used as the thermal hardener (b2), the thermal hardener is in terms of easily adjusting the adhesive force E of the film adhesive before curing to the semiconductor wafer within the above range. (b2) The softening point or the glass transition temperature is preferably high.

The weight-average molecular weight of the thermosetting agent (b2) is preferably 60 to 30,000, for example.

The thermosetting agent (b2) may be used singly, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition and the film-shaped adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass, and more preferably 1 part by mass based on 100 parts by mass of the content of the epoxy resin (b1). Parts to 200 parts by mass. When the aforementioned content of the thermosetting agent (b2) is equal to or more than the aforementioned lower limit value, the curing of the film-shaped adhesive is more easily performed. In addition, since the content of the thermosetting agent (b2) is equal to or less than the aforementioned upper limit value, the moisture absorption of the film-shaped adhesive is reduced, and the reliability of the package obtained by using the film-shaped adhesive composite sheet is further improved.

In the adhesive composition and the film-like adhesive, the content of the epoxy-based thermosetting resin (b) (that is, the epoxy resin (b1) and the thermosetting) with respect to 100 parts by mass of the content of the polymer component (a) The total content of the agent (b2)) is preferably 50 parts by mass to 1,000 parts by mass, more preferably 100 parts by mass to 900 parts by mass, and even more preferably 150 parts by mass to 870 parts by mass. When the aforementioned content of the epoxy-based thermosetting resin (b) is in such a range, it is easier to separate the semiconductor wafer provided with the film-shaped adhesive from the support sheet at the time of pickup.

In one aspect, the content of the epoxy-based thermosetting resin (b) is preferably 20% by mass to 80% by mass based on the total mass of the adhesive composition and the film-like adhesive.

In order to improve various physical properties of the film-shaped adhesive, the film-shaped adhesive may contain, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components that do not correspond to these. ingredient.

Among the other components contained in the film-like adhesive, preferable ones include, for example, a hardening accelerator (c), a filler (d), a coupling agent (e), a cross-linking agent (f), and energy ray hardenability. Resin (g), photopolymerization initiator (h), general additive (i), and the like.

That is, as one aspect, the film-shaped adhesive of the film-shaped adhesive composite sheet of the present invention contains: a polymer component (a); an epoxy-based thermosetting resin (b); and a member selected from a hardening accelerator (c ), Filler (d), coupling agent (e), cross-linking agent (f), energy ray hardening resin (g), photopolymerization initiator (h), and general additive (i) Of at least one ingredient.

(Hardening accelerator (c))

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

Examples of the preferred hardening accelerator (c) include tertiary grades such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. Amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Imidazoles such as 5-hydroxymethylimidazole (e.g., imidazole having at least one hydrogen atom substituted with a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (e.g., at least one hydrogen Phosphine with an atom substituted by an organic group); tetraphenylboronate such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The hardening accelerator (c) contained in the adhesive composition and the film-shaped adhesive may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

When the hardening accelerator (c) is used, the content of the hardening accelerator (c) in the adhesive composition and the film-like adhesive is 100 parts by mass with respect to the content of the epoxy-based thermosetting resin (b). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. Since the content of the hardening accelerator (c) is equal to or more than the aforementioned lower limit value, the effect obtained by using the hardening accelerator (c) is more significantly obtained. In addition, since the content of the hardening accelerator (c) is equal to or less than the aforementioned upper limit value, for example, the highly polar hardening accelerator (c) is inhibited from moving to the adherend in the film-shaped adhesive under high temperature and high humidity conditions. Then the effect of segregation on the interface side becomes higher, and the reliability of the package obtained by using the film-like adhesive composite sheet is further improved.

(Filling material (d))

The film-shaped adhesive contains a filler (d), and the adjustment of the thermal expansion coefficient of the film-shaped adhesive is facilitated. The film-shaped adhesive is optimized for the object to be attached to the film-shaped adhesive, and the film-shaped adhesive is used. The reliability of the package obtained by the adhesive compound sheet is further improved. In addition, by including the filler (d) in the film-shaped adhesive, the moisture absorption of the film-shaped adhesive after curing can be reduced, or the heat dissipation can be improved.

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

Preferred inorganic fillers include, for example, powders of silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, iron white, silicon carbide, boron nitride, etc .; these inorganic fillers are made into a spherical shape. Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers and the like.

Among these, the inorganic filler is preferably silicon dioxide or aluminum oxide.

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

When the filler (d) is used, the content of the filler (d) in the adhesive composition relative to the total content (total mass) of all components other than the solvent (that is, the filler (d) relative to the film) The content of the total mass of the adhesive agent is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content of the filler (d) is in such a range, adjustment of the above-mentioned thermal expansion coefficient becomes easier.

(Coupling agent (e))

The film-shaped adhesive contains the coupling agent (e) to improve adhesion and adhesion to the adherend. In addition, when the film-shaped adhesive contains the coupling agent (e), the cured product of the film-shaped adhesive is improved in water resistance without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

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

Examples of the preferable silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrisilane. Ethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldi Ethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinepropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, imidazolesilane, epoxy-containing oligomers, etc.

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

When the coupling agent (e) is used, the content of the polymer component (a) and the epoxy-based thermosetting resin (b) in the adhesive composition and the film-like adhesive is 100 parts by mass. The content of the mixture (e) is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass.

As the aforementioned content of the coupling agent (e) is above the aforementioned lower limit, the dispersion of the filler (d) in the resin is improved or the adhesion of the film-like adhesive to the adherend is improved. Effect of coupling agent (e). In addition, by the aforementioned content of the coupling agent (e) being equal to or lower than the aforementioned upper limit value, the generation of outgassing is further suppressed.

(Crosslinking agent (f))

In the case of using the acrylic resin and other functional groups having a functional group such as vinyl, (meth) acryl, amine, hydroxyl, carboxyl, and isocyanate groups, which can be bonded to other compounds, as the polymer component (a), The adhesive agent composition and the film-like adhesive agent may contain a crosslinking agent (f) for bonding the functional group to another compound to perform crosslinking. By performing crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the film-like adhesive can be adjusted.

Examples of the crosslinking agent (f) include an organic polyisocyanate compound, an organic polyimide compound, a metal chelate-based cross-linking agent (that is, a cross-linking agent having a metal chelate structure), and an aziridine system. Cross-linking agents (that is, cross-linking agents having aziridinyl) and the like.

Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds are collectively referred to simply as "aromatic polyisocyanate compounds"); the aromatic Terpolymers, isocyanurates, and adducts of group polyisocyanate compounds; terminal isocyanate urethane prepolymers and the like obtained by reacting the aforementioned aromatic polyisocyanate compounds and the like with polyol compounds. The aforementioned "adduct" refers to a low-molecular-weight compound such as the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. Examples of the reactant of the active hydrogen compound include xylene diisocyanate adducts of trimethylolpropane as described below, and the like. The "terminal isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and having an isocyanate group at the terminal portion of the molecule.

Specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4- Xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene di Isocyanates; isophorone diisocyanates; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate, hexamethylene diisocyanate and xylylene A compound obtained by adding one or two or more diisocyanates to all or part of the hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; a diisocyanate such as an amino acid.

Examples of the organic polyimide compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), and trimethylolpropane-tri-β-nitrogen. Propidyl propionate, tetramethylol methane-tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxamide) triethylene melamine Wait.

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

The cross-linking agent (f) contained in the adhesive composition and the film-shaped adhesive may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of these may be arbitrarily selected.

When a crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the content of the polymer component (a). Parts, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.5 parts by mass to 5 parts by mass. Since the aforementioned content of the crosslinking agent (f) is above the aforementioned lower limit value, the effect obtained by using the crosslinking agent (f) is more significantly obtained. In addition, an excessive use of the crosslinking agent (f) is suppressed by the content of the crosslinking agent (f) being equal to or less than the aforementioned upper limit value.

(Energy ray curable resin (g))

The film-shaped adhesive contains an energy ray-curable resin (g), and its properties can be changed by irradiating the energy ray.

The energy ray-curable resin (g) has a property of being cured (polymerized) by irradiating energy rays.

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

Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (methyl) Acrylate), dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylates containing chain aliphatic skeletons such as (meth) acrylates; cyclic aliphatic skeletons containing dicyclopentyl di (meth) acrylate, tricyclodecane dimethylol diacrylate, etc. (Meth) acrylates; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylates; oligopolyester (meth) acrylates; (meth) acrylate amino groups Formate oligomers; epoxy-modified (meth) acrylates; polyether (meth) acrylates other than the aforementioned polyalkylene glycol (meth) acrylates; itaconic acid oligomers; and the like.

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

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

The content of the energy ray-curable resin (g) is preferably 1% to 95% by mass, more preferably 3% to 90% by mass, and even more preferably 5% to 85% by mass relative to the total mass of the adhesive composition. quality%.

(Photopolymerization initiator (h))

When the adhesive composition contains the energy ray-curable resin (g), the photopolymerization initiator (h) may be contained in order to efficiently perform 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 benzoic acid methyl ester, and benzoin. Benzoin compounds such as dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethyl Acetophenone compounds such as alkane-1-ones; bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, 2,4,6-trimethylbenzylidenediphenylphosphine oxide Isofluorenyl phosphine oxide compounds; thioether compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketoalcohol compounds such as 1-hydroxycyclohexylphenyl ketone; and azobisisobutyronitrile Nitrogen compounds; Titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diethylfluorene; benzoin; benzophenone; benzophenone ; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone; 1- Quinone compounds such as chloroanthraquinone and 2-chloroanthraquinone.

Examples of the photopolymerization initiator (h) include a photosensitizer such as an amine.

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

In the adhesive composition, the content of the photopolymerization initiator (h) is preferably 0.1 to 20 parts by mass, and more preferably 1 part by mass with respect to 100 parts by mass of the content of the energy ray-curable resin (g). To 10 parts by mass, particularly preferably 2 to 5 parts by mass.

(General additive (i))

The general-purpose additive (I) may also be known, and may be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include plasticizers, antistatic agents, antioxidants, and colorants (dye, pigment). , Getter, etc.

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

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

(Solvent)

The adhesive composition preferably further contains a solvent. The solvent-containing adhesive composition system has good operability.

The solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (also known as 2-methylpropane-1-ol), Alcohols such as 1-butanol; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone; ethers such as tetrahydrofuran; fluorenamines such as dimethylformamide, N-methylpyrrolidone (i.e., with fluoramine Bond compounds) and so on.

The solvent contained in the adhesive composition may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

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

[Manufacturing method of adhesive composition]

The adhesive agent composition is obtained by blending each component constituting the adhesive agent composition.

The order of adding the ingredients is not particularly limited, and two or more kinds of ingredients may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any formulation component other than the solvent, and the formulation component may be diluted before use, or any formulation component other than the solvent may not be diluted in advance, and the solvent and the These preparation ingredients are mixed and used.

There is no particular limitation on the method of mixing the components during the preparation, as long as it is appropriately selected from the following methods: a method of mixing by rotating a stirrer or a stirring wing, etc .; a method of mixing using a mixer; and applying an ultrasonic wave to mix And other well-known methods.

The temperature and time during the addition and mixing of the components are not particularly limited as long as the prepared components do not deteriorate, as long as they are appropriately adjusted, the temperature is preferably 15 ° C to 30 ° C.

In the film-shaped adhesive composite sheet of the present invention, it is preferable that the support sheet is composed of only a substrate, and a film-shaped adhesive is provided for the substrate to be in direct contact. When such a support sheet does not have an adhesive layer and the like, and a film-like adhesive is directly provided on the substrate, the components in the film-like adhesive migrate to other layers on the substrate such as the adhesive layer or the other way around. On the other hand, the migration of components in such other layers to the interlayer movement of constituent components such as a film-like adhesive is suppressed. Therefore, it is possible to significantly suppress the occurrence of step abnormalities in manufacturing a semiconductor device or decrease the reliability of the semiconductor package.

In general, when a film-like adhesive composite sheet is used without a pressure-sensitive adhesive layer, when the semiconductor wafer is separated from the support sheet while the film-shaped adhesive is attached to the semiconductor wafer, double crystal grains are easily generated. However, according to the film-shaped adhesive composite sheet of the present invention, even when the composite sheet does not have an adhesive layer, the generation of double crystal grains is suppressed.

<< Making method of film-like adhesive compound sheet >>

The film-like adhesive composite sheet of the present invention can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

For example, in the case of laminating an adhesive layer on a substrate when manufacturing a support sheet, the adhesive layer can be laminated by coating the above-mentioned adhesive composition on the substrate and drying it if necessary.

For example, when a film-shaped adhesive is laminated on the adhesive layer laminated on the substrate, as an aspect, an adhesive composition can be applied on the adhesive layer and directly formed on the aforementioned adhesive layer. Membrane adhesive. That is, in the case of forming a laminated structure of two consecutive layers, any composition may be used, and another composition may be directly applied to the layer formed of the foregoing composition to newly form a layer. In addition, as another aspect, the back-laminated layer of these two layers may be formed in advance on another release film using the aforementioned composition, and the side of the formed layer that is in contact with the release film is the opposite side The exposed surface of is bonded to the exposed surfaces of the remaining layers already formed, thereby forming a continuous two-layer laminated structure. In this case, the composition is preferably applied to a release-treated surface of a release film. The release film may be removed as necessary after forming a laminated structure.

For example, a film-shaped adhesive compound sheet (that is, a film of a support sheet as a substrate and a laminate of an adhesive layer) produced by laminating an adhesive layer on a substrate and laminating a film-shaped adhesive on the aforementioned adhesive layer. In the case of adhesive-like adhesive composite sheet), a film-like adhesive composite sheet can be obtained by coating an adhesive composition on a substrate and drying it if necessary, thereby laminating an adhesive layer on the substrate, and An adhesive composition is coated on the release film, and if necessary dried, a film-shaped adhesive is formed on the release film, and the exposed surface of the film-shaped adhesive and the adhesive layer laminated on the substrate are exposed. The surface is bonded, and the film-shaped adhesive is laminated on the adhesive layer.

In addition, when the adhesive layer is laminated on the substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition may be applied on the release film and dried as necessary. Thereby, an adhesive layer is formed on the release film, and the exposed surface of the adhesive layer is adhered to one surface of the substrate, thereby laminating the adhesive on the substrate.

In either method, the release film may be removed at any timing after the target laminated structure is formed.

In this way, layers other than the base material constituting the film-like adhesive composite sheet can be laminated by a method previously formed on the release film and bonded to the surface of the target layer, so as long as the layer using this step is appropriately selected as needed, A film-like adhesive composite sheet may be produced.

The film-shaped adhesive composite sheet is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film-shaped adhesive) on the opposite side to the support sheet in the film-shaped adhesive composite sheet. Therefore, a film-like adhesive composite sheet is also obtained by coating the release film (preferably the release-treated surface of the release film) with a support for forming and forming a film-like adhesive composite sheet. The composition of the outermost layer (ie, the adhesive composition, etc.) on the opposite side of the sheet side is dried as necessary to form a layer constituting the outermost layer on the release film, and the release layer and the release film The contact side is an exposed surface on the opposite side, and the remaining layers are laminated by any of the methods described above, and the peeling film is not removed, and the bonded state is maintained.

<< Method for Manufacturing Semiconductor Device >>

A method for manufacturing a semiconductor device according to an embodiment of the present invention uses the film-shaped adhesive composite sheet, and includes attaching the film-shaped adhesive composite sheet to a plurality of divided semiconductors through the film-shaped adhesive. Wafers (hereinafter sometimes referred to as "attachment steps"); the support sheet attached to the aforementioned film-like adhesive composite sheet of the semiconductor wafer is separated from the side opposite to the side where the film-like adhesive is provided Apply force to the film-shaped adhesive by the support sheet, thereby cutting the film-shaped adhesive (hereinafter sometimes referred to simply as the "cutting step"); and cutting the semiconductor wafer and a die attached to the semiconductor wafer The film-like adhesive after separation is separated from the support sheet (hereinafter sometimes referred to simply as "separation step").

According to the aforementioned manufacturing method, by using the aforementioned film-shaped adhesive composite sheet, a semiconductor device to which the film-shaped adhesive is affixed can be separated from the support sheet by using a simplified method to suppress the occurrence of step abnormalities when manufacturing a semiconductor device.

<Attachment procedure>

In the aforementioned attaching step, the aforementioned film-like adhesive composite sheet is attached to a plurality of divided semiconductor wafers via the aforementioned film-like adhesive. In this step, a film-shaped adhesive in a film-shaped adhesive composite sheet is attached to the back surface of a plurality of semiconductor wafers.

The divided plurality of semiconductor wafers can be produced, for example, by forming grooves from the surface of the semiconductor wafer opposite to the surface on which the film-like adhesive compound is attached (sometimes referred to as the back surface), and The back is ground until it reaches the groove. As a method of forming the aforementioned grooves, for example, a method of scribe a semiconductor wafer using a blade to form a groove (ie, dicing by a blade); a method of scribe a semiconductor wafer by laser irradiation to form a groove ( (Ie, laser cutting); a method of forming a groove by spraying a semiconductor wafer by spraying water containing an abrasive (ie, water cutting), and the like.

In addition, a plurality of divided semiconductor wafers can also be produced by irradiating laser light in the infrared region in a manner focused on the focus provided inside the semiconductor wafer, and forming a modified layer inside the semiconductor wafer. Polish the aforementioned back surface of the semiconductor wafer, and then apply force to the polished semiconductor wafer on the aforementioned back surface, or apply the force during polishing to the aforementioned semiconductor wafer during the aforementioned back grinding, thereby forming the modified layer. The part divides the aforementioned semiconductor wafer.

<Cutting step>

In the cutting step, after the attaching step, the support sheet attached to the film-shaped adhesive compound sheet of the semiconductor wafer is separated from the side opposite to the side on which the film-shaped adhesive is provided. The support sheet applies force to the film-shaped adhesive, and cuts the film-shaped adhesive. Hereinafter, a method for manufacturing a semiconductor device according to an embodiment of the present invention will be described with reference to the drawings. (A) to (c) of FIG. 1 are schematic views showing an embodiment from the cutting of the film-like adhesive to the separation from the support sheet of a semiconductor wafer in the manufacturing method of the present invention. Sectional view. In (a) to (c) of FIG. 1, only the structure regarding a film-shaped adhesive compound sheet is shown in cross section.

As shown in (a) of FIG. 1, the film-shaped adhesive 12 of the film-shaped adhesive composite sheet 1 is attached to the back surface 9 b of the plurality of semiconductor wafers 9 by the aforementioned attaching step. Furthermore, in this step, the semiconductor wafer manufacturing apparatus (not shown in the general drawing) is placed on top of the semiconductor wafer 81 on the support sheet 11 in the film-shaped adhesive composite sheet 1. A surface (sometimes referred to as a back surface) 11b opposite to a surface (sometimes referred to as a surface) 11a on the side where the film-like adhesive 12 is provided.

When the support sheet 11 is composed only of a substrate, the film-like adhesive composite sheet 1 is a sheet obtained by laminating a substrate and a film-like adhesive 12, and the film-like adhesive 12 is in contact with the substrate. The surface on the opposite side is attached to the back surface 9 b of the semiconductor wafer 9.

When the support sheet 11 is a sheet obtained by laminating a base material and an adhesive, the film-like adhesive composite sheet 1 has a base material, an adhesive layer, and a film-like adhesive 12 laminated in this order, The surface of the agent 12 on the side opposite to the side in contact with the adhesive layer is attached to the back surface 9 b of the semiconductor wafer 9.

In this step, as shown in FIG. 1 (b), a force is applied to the support sheet 11 in the film-like adhesive composite sheet 1 from the back surface 11 b of the support sheet 11, so as to sandwich the support sheet 11 through the support sheet 11. The film-like adhesive 12 applies a force. Here, an example is shown: a protrusion (ie, a pin) 811 protrudes from the upper top portion 81, and a top portion of the protrusion 811 lifts the support sheet 11 from the back surface 11b of the support sheet 11, thereby interposing the support sheet 11 pair The film-shaped adhesive 12 is urged in a protruding direction of the protrusion 811. At this time, it is possible to appropriately adjust the protruding conditions (ie, the amount of pushing up), the protruding speed (ie, the pushing speed), the holding time of the protruding state (ie, the waiting time for lifting), and other lifting conditions. Here, the number of the protrusions 811 on the support sheet 11 is shown as five, but it may be one or two or more. The number of the protrusions 811 may be appropriately selected.

If a force is applied to the film-like adhesive 12 in this manner, since the film-like adhesive composite sheet 1 is used, it is possible to suppress the occurrence of step abnormalities while suppressing the occurrence of abnormalities in the film while suppressing the occurrence of step abnormalities due to the shear force generated by the top of the protrusion 811. The adhesive agent 12 is cut. More specifically, the film-shaped adhesive 12 can be cut at room temperature at a target portion, that is, only a portion surrounding the person to be separated from the support sheet 11 as the semiconductor wafer 9 is located at a normal temperature. Further, for example, the step of cutting off the film-shaped adhesive 12 may be performed without separately providing a step of cutting the film-shaped adhesive 12 by laser or a step of cutting the film-shaped adhesive 12 by expanding the film-shaped adhesive 12 as the main purpose. In the case of step.

<Separation step>

In the aforementioned separating step, as shown in FIG. 1 (c), after the aforementioned cutting step, the semiconductor wafer 9 and the cut film-shaped adhesive 12 attached to the semiconductor wafer 9 are separated from the support sheet 11. (I.e. pick up). This step is usually performed immediately after the aforementioned cutting step. Here, an example is shown in which the semiconductor wafer 9 is pulled up by the pulling portion 82 of the manufacturing apparatus of the semiconductor device, whereby the film-shaped adhesive 12 adhered to the semiconductor wafer 9 is cut from the support sheet. 11 separation. The method of pulling up the semiconductor wafer 9 in this manner may be a known method, and examples thereof include a method of sucking the surface of the semiconductor wafer 9 by a vacuum chuck and pulling up.

When the semiconductor wafer 9 is pulled up in this manner, since the film-like adhesive composite sheet 1 is used, the film-like adhesive 12 can be peeled from the support sheet 11 while suppressing the occurrence of step abnormalities. More specifically, the phenomenon that the portion corresponding to the target semiconductor wafer 9 in the film-shaped adhesive 12 is peeled from the support sheet 11 and the portion corresponding to the semiconductor wafer 9 outside the target in the film-shaped adhesive 12 is removed from the support is suppressed. The sheet 11 is peeled. In addition, since the film-like adhesive 12 has been cut at a predetermined position, the lifted semiconductor wafer 9 and the film-like adhesive 12 are separated from the support sheet 11 together.

In the manufacturing method of the present invention, a semiconductor wafer that is separated (that is, picked up) together with a film-shaped adhesive can be used. Later, the same method as in the conventional method is used, that is, the aforementioned method is performed by using the film-shaped adhesive. The semiconductor wafer is formed on the circuit surface of the substrate, and a semiconductor device is manufactured. For example, the aforementioned semiconductor wafer is bonded to the circuit surface of the substrate with a film-shaped adhesive, and if necessary, one or more semiconductor wafers are laminated on the semiconductor wafer, and after wire bonding is performed, the whole is sealed with resin, thereby Made into a semiconductor package. Then, it is only necessary to produce a target semiconductor device using the semiconductor package.

As one aspect, the method for manufacturing a semiconductor device of the present invention includes: attaching the film-like adhesive composite sheet to a plurality of divided semiconductor wafers through the film-like adhesive; The support sheet in the film-shaped adhesive composite sheet is configured to cut the film-shaped adhesive by applying force to the film-shaped adhesive through the support sheet from a side opposite to a side on which the film-shaped adhesive is provided. The semiconductor wafer and the film-shaped adhesive adhered to the semiconductor wafer are separated from the support sheet; the semiconductor wafer separated from the support sheet by the film-shaped adhesive is on the circuit surface of the substrate Die bonding; and if necessary, laminating more than one semiconductor wafer to the aforementioned semiconductor wafer, wire bonding, and overall sealing with resin to obtain a semiconductor package.

The manufacturing method of the semiconductor device of the present invention is not limited to the above-mentioned method described with reference to (a) to (c) in FIG. 1, and may also be within the above-mentioned method within a range that does not impair the efficacy of the present invention. Change, delete, or add a part of the configuration.

For example, as a method of applying force to the film-like adhesive 12 via the support sheet 11, a method of applying force to the film-like adhesive 12 by lifting the support sheet 11 with the protrusion 811 has been described so far. Other methods include, for example, a method of applying force to the film-shaped adhesive 12 by sliding the support sheet 11 up by a slider instead of the protrusion 811.

FIG. 2 (a) and FIG. 2 (b) are cross-sectional views schematically illustrating another embodiment in which the film-shaped adhesive is cut by applying force to the film-shaped adhesive. In addition, in (a) in FIG. 2 and (b) in FIG. 2, the same constituent elements as those shown in (a) to (c) in FIG. 1 are denoted as in FIG. 1. (A) to (c) in FIG. 1 are the same symbols, and detailed descriptions of the constituent elements are omitted. This situation is the same in the figures after (a) in FIG. 3 and (b) in FIG. 3.

The method shown here replaces the cutting method of the film-like adhesive with the one described with reference to (b) in FIG. 1.

In the case of applying this embodiment, the attaching step is also first performed by the same method as the case described with reference to (a) in FIG. 1.

Next, for the support sheet 11 in the film-shaped adhesive composite sheet 1, the film-shaped adhesive 12 is urged on the back surface 11b of the support sheet 11 via the support sheet 11. However, in this embodiment, the movement of the slider 812 shown in FIG. 2 (a) and FIG. 2 (b) is not the same as shown in FIG. 1 (b) in the upper top 81. The protrusion 811 protrudes, and the support sheet 11 is lifted from the back surface 11 b of the support sheet 11.

In this embodiment, as shown in (a) of FIG. 2, the surface 812 a of the slider 812 protruding from the upper top portion 81 is brought into contact with the back surface 11 b of the support sheet 11. At this time, the surface 812a of the slider 812 is not parallel to the back surface 11b of the support sheet 11 before the cutting step as shown in FIG. 1 (a). Therefore, the support sheet 11 is forced from the back surface 11b of the support sheet 11 in a direction orthogonal to the surface 812a of the slider 812, that is, an oblique direction instead of a vertical direction, thereby the top height of the film-shaped adhesive 12 Make a difference. However, similarly to the case of (b) in FIG. 1, the film-shaped adhesive 12 is urged through the support sheet 11. Thereby, in the region where the top height above the film-like adhesive 12 is high, and in the region where the semiconductor wafer 9 is not attached (the first region 121 in (a) in FIG. 2), the top is accompanied by The shearing force generated can cut the film-like adhesive 12 while suppressing the occurrence of step abnormalities.

When the slider 812 is pushed upward, the protrusion conditions of the slider 812 (ie, the amount of pushing up), the inclination angle (that is, the speed of pushing up), and the moving speed (that is, the waiting time for lifting) can be appropriately adjusted.

In this embodiment, as shown in FIG. 2 (b), the slider 812 is moved in a direction parallel to the back surface 11 b of the support sheet 11 that is not topped. Thereby, the top position of the support sheet 11 is moved. After the upper and upper positions are moved, in a region where the top height above the film-like adhesive 12 is high, a region where the semiconductor wafer 9 is not attached (the second region 122 in (b) in FIG. 2) The film-like adhesive 12 can be cut while suppressing the occurrence of step abnormalities by the shearing force accompanying the top-up.

By the shearing force accompanying the movement of the slider 812, the film adhesive 12 is suppressed in the same manner as described with reference to (a) to (c) in FIG. 1. The abnormality of the step is cut off.

Thereafter, the separation step can be performed by the same method as that described with reference to (a) in FIG. 1.

However, it is generally described with reference to (a) in FIG. 2 and (b) in FIG. 2 as described above with reference to (a) to (c) in FIG. 1 The general pin-on-top method is a film-shaped adhesive with high cutting effect. Therefore, it is preferable to select which method to take into consideration, for example, the Young's coefficient (A) of the support sheet or the elongation at break (C) of the film-like adhesive, and the strength-related characteristics are selected.

As described above, according to the method for manufacturing a semiconductor device according to an embodiment of the present invention, in the cutting step, the film-shaped adhesive can be cut at a target portion, so that the film-shaped adhesive can be prevented from being cut. Defective separation (lifting) of the semiconductor wafer.

In addition, according to the method for manufacturing a semiconductor device according to an embodiment of the present invention, in the aforementioned separation step, the target portion of the film-like adhesive is peeled from the support sheet, so that occurrence of separation (lifting) defects of the semiconductor wafer is suppressed. In addition, peeling off parts of the film-shaped adhesive from the support sheet is suppressed, so that not only the target semiconductor wafer but also a semiconductor wafer adjacent to the target semiconductor wafer is simultaneously suppressed from being separated from the support sheet together with the film-shaped adhesive. Generation of grains.

Thus, according to the present invention, a simplified method can be used to suppress the occurrence of step abnormalities to manufacture a semiconductor device.

When the film-shaped adhesive compound sheet of the present invention is not used, it may be impossible to suppress the occurrence of abnormalities in the steps shown below when manufacturing a semiconductor device.

(A) and (b) of FIG. 3 are schematic diagrams showing examples of a film-like adhesive composite sheet and a semiconductor wafer in a manufacturing process of a semiconductor device when a conventional film-like adhesive composite sheet is used. A cross-section view.

When the film-shaped adhesive composite sheet 7 shown here is used, as shown in FIG. 3 (a), even if the film-shaped adhesive 72 is urged through the support sheet 71, the support sheet 71 is greatly increased. The ground is deformed, and the pickup force is not transmitted to the film-shaped adhesive, and the film-shaped adhesive 72 is not cut. Furthermore, when the semiconductor wafer 9 is pulled up, the film-shaped adhesive 72 is peeled from the semiconductor wafer 9 and is kept laminated to support. Tablet 71. As a result, as shown in FIG. 3 (b), the lifting failure of the semiconductor wafer 9 occurred.

Such a step abnormality is likely to occur, for example, in the case of the film-like adhesive composite sheet 7 in which the Young's coefficient (A) (MPa) of the support sheet is small, or the thickness (B) (mm) of the support sheet is small. , Or both the Young's coefficient (A) of the support sheet and the thickness (B) of the support sheet are small, as a result, the aforementioned product (A × B) is less than 4 MPa. mm.

FIGS. 4 (a) and 4 (b) are schematic diagrams showing the state of a film-like adhesive compound sheet and a semiconductor wafer during the manufacturing process of a semiconductor device when a conventional film-like adhesive compound sheet is used. A cross-sectional view of another aspect.

In the case where the film-shaped adhesive composite sheet 7 shown here is used, even if the film-shaped adhesive 72 is urged through the support sheet 71 as shown in FIG. 4 (a), the support sheet 71 is not easily deformed. . Therefore, the area around the target film-shaped adhesive corresponding to the semiconductor wafer is also lifted, and the force at the time of pickup is not transmitted to the film-shaped adhesive, and the film-shaped adhesive 72 is not cut. When the semiconductor wafer 9 is pulled up, the film-like adhesive 72 is peeled from the semiconductor wafer 9 and is kept laminated on the support sheet 71. As a result, as shown in FIG. 3 (b), the lifting failure of the semiconductor wafer 9 occurs.

Such a step abnormality is easily caused, for example, when the film-like adhesive compound sheet 7 has a large Young's coefficient (A) (MPa) of the support sheet, or a thickness (B) (mm) of the support sheet. Large, or both the Young's coefficient (A) of the support sheet and the thickness (B) of the support sheet are large, as a result, the aforementioned product (A × B) is greater than 150 MPa. mm.

Moreover, the abnormal steps described with reference to (a) in FIG. 3 and (b) in FIG. 3 to (a) in FIG. 4 and (b) in FIG. 4 are examples, and depending on the situation, sometimes Generate other steps exception.

On the other hand, when the film-shaped adhesive composite sheet of the present invention is used, the occurrence of abnormalities in such steps is suppressed, and as a result, a semiconductor device can be manufactured at a lower cost by a more simplified method than in the past.

As one aspect, a film-like adhesive composite sheet according to an embodiment of the present invention is provided with a hardening film-like adhesive on a support sheet, and the support sheet has a substrate, and the thickness of the support sheet is 20 μm to 200 μm. The thickness is preferably 25 μm to 150 μm, more preferably 30 μm to 100 μm, and even more preferably 38 μm to 80 μm. The thickness of the film adhesive is 1 μm to 60 μm, preferably 3 μm to 25 μm, and more preferably 5 μm to 15 μm. The Young's coefficient is 50 MPa to 5000 MPa, preferably 100 MPa to 4000 MPa, more preferably 150 MPa to 3000 MPa, and even more preferably 170 MPa to 2250 MPa; the product of the Young's coefficient of the aforementioned support sheet and the thickness of the aforementioned support sheet is 4 MPa. mm to 150MPa. mm, preferably 13.6 MPa. mm to 112.5MPa. mm; The hardening film-shaped adhesive has the following characteristics: When the film-shaped adhesive before curing is laminated to form a laminated body having a total thickness of 200 μm, the elongation at break of the laminated body is 1% to 2000%, It is preferably 30% to 1200%, more preferably 40% to 1100%, particularly preferably 45% to 1050%, and has the following characteristics: the breaking strength of the aforementioned laminated body is 0.1 MPa to 17 MPa, and preferably 0.2 MPa to 15 MPa, more preferably 0.4 MPa to 13 MPa; the aforementioned hardening film-shaped adhesive has the following characteristics: when the film-shaped adhesive before curing is adhered to a semiconductor wafer, the adhesive force becomes 3N / 24mm or more and 15N / 24mm or less, It is preferably 3N / 24mm or more and 11N / 24mm or less, more preferably 4N / 24mm or more and 11N / 24mm or less, and particularly preferably 4N / 24mm or more and 10N / 24mm or less. The hardening film-shaped adhesive has the following characteristics: The value of (the aforementioned elongation at break × the aforementioned breaking strength) is 0.0005 or more and 0.80 or less, preferably 0.0006 or more and 0.50 or less, and more preferably 0.0007 or more and 0.10 or less.

As another aspect, the film-shaped adhesive composite sheet according to an embodiment of the present invention is provided with a hardening film-shaped adhesive on a support sheet, and the support sheet has a substrate, and the thickness of the support sheet is 20 μm to 200 μm. , Preferably 25 μm to 150 μm, more preferably 30 μm to 100 μm, particularly preferably 38 μm to 80 μm; the aforementioned substrate is a substrate composed of polyethylene terephthalate; and the thickness of the aforementioned hardening film-like adhesive 1 μm to 60 μm, preferably 3 μm to 25 μm, more preferably 5 μm to 15 μm; the aforementioned hardening film-shaped adhesive contains: a polymer component (a), an epoxy-based thermosetting resin (b), and a material selected from the group consisting of hardening Composition of accelerator (c), filler (d), coupling agent (e), cross-linking agent (f), energy ray hardening resin (g), photopolymerization initiator (h), and general additive (i) At least one component of the group; the polymer component (a) is an acrylic resin; the epoxy-based thermosetting resin (b) includes a resin selected from a bisphenol A-type epoxy resin and a polyfunctional aromatic epoxy At least one resin in the group consisting of resin and dicyclopentadiene epoxy resin; The total mass of the curable film-shaped adhesive is that the content of the polymer component (a) is 5 to 85% by mass, preferably 7 to 80% by mass; The content is 100 parts by mass, and the content of the epoxy-based thermosetting resin (b) is 50 to 1,000 parts by mass, preferably 100 to 900 parts by mass, and more preferably 150 to 870 parts by mass; The product of the Young's coefficient of the support sheet and the thickness of the aforementioned support sheet is 4 MPa. mm to 150MPa. mm, preferably 13.6 MPa. mm to 112.5MPa. mm.

As another aspect, a method for manufacturing a semiconductor device according to an embodiment of the present invention includes: attaching the film-shaped adhesive composite sheet to a plurality of divided semiconductor wafers through the film-shaped adhesive; The support sheet in the film-shaped adhesive composite sheet attached to the semiconductor wafer is urged to the film-shaped adhesive through the support sheet from the side opposite to the side on which the film-shaped adhesive is provided, whereby Cutting the film-shaped adhesive; and separating the semiconductor wafer and the film-shaped adhesive adhered to the semiconductor wafer from the support sheet.

The manufacturing method may further include: bonding the semiconductor wafer separated from the support sheet to the circuit surface die of the substrate by the film-shaped adhesive; and laminating more than one semiconductor wafer on the semiconductor wafer, if necessary, After the wire bonding is performed, the whole is sealed with a resin, thereby obtaining a semiconductor package.

[Example]

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

The components for producing the adhesive composition are shown below.

． Polymer composition

(a) -1: Acrylic resin ("Coponyl N-2359-6" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

． Epoxy resin

(b1) -1: Liquid bisphenol A type epoxy resin ("JER834" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 250 g / eq, weight average molecular weight 470).

(b1) -2: Polyfunctional aromatic type (terphenyl) epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167 g / eq, softening point 54 ° C, weight average molecular weight 1200).

(b1) -5: Dicyclopentadiene type epoxy resin ("ADEKA RESIN EP-4088L" manufactured by ADEKA Corporation, epoxy equivalent 165 g / eq).

． Heat hardener

(b2) -1 Biphenyl type phenol resin ("MEH-7851-SS" manufactured by Meiwa Chemical Co., Ltd., softening point: 67 ° C).

． Hardening accelerator

(c) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.).

． Filler

(d) -1: Spherical silicon dioxide ("SC2050" manufactured by Admatechs).

． Coupling agent

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

<Manufacture of support sheet>

A support sheet for producing a film-like adhesive composite sheet is shown below.

Support sheet (1): Prepare 2-ethylhexyl acrylate (hereinafter referred to as "2EHA") (65 parts by mass), methyl methacrylate (hereinafter referred to as "MMA") (25 parts by mass), and Acrylic resin (weight average molecular weight 400,000, glass transition temperature -28 ° C) ((a) -2) 250 mass by copolymerization of 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (10 parts by mass) Parts and cross-linking agent ((f) -1: BHS-8515: trade name, manufactured by Toyo Ink Manufacturing Co., toluene diisocyanate-based compound) 50.27 parts by mass of a solution dissolved in 175.13 parts of toluene, and the aforementioned solution was coated with A light release sheet (product name "SP-PET38 1031" (thickness: 38 µm)) manufactured by Lintec Corporation as a substrate was applied so as to have a thickness of 20 μm. The substrate was peeled after the above coating film was laminated four times to obtain a thickness. 80 μm support sheet (1).

Support sheet (2): low density PE (Polyethylene; polyethylene) / PP (Polypropylene; polypropylene) / low density PE two three-layer substrates with a total thickness of 80 μm, and one side is smooth and shiny, the other single The surface is a plurality of plastic sheets with satin processing for the purpose of blocking resistance.

Support sheet (3): a light release sheet (product name "SP-PET38 1031", thickness: 38 m) manufactured by Lintec.

Support sheet (4): a light release sheet (product name "SP-PET50 1031", thickness 50 μm) manufactured by Lintec.

Support sheet (5): A solution mixture of 82 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, and 15 parts of acrylamide was subjected to solution polymerization in 100 parts of ethyl acetate to obtain an acrylic system having a number average molecular weight of 700,000. Copolymer polymer. Next, to 100 parts of the obtained polymer, 20 parts of an ester-based plasticizer (made by Dainippon Ink Chemical Industry Co., Ltd., dioctyl terephthalate) and a melamine-based crosslinking agent (made by Dainippon Ink Chemical Industry Co., Ltd.) were added. , J-820-60N) 0.1 part and isocyanate cross-linking agent (manufactured by Polyurethane Industry Co., Ltd., Japan, Coronate HL) 3 parts, coated with light peeling made by Lintec company so that the thickness of the coating film becomes 20 μm Sheet (product name "SP-PET38 1031" (thickness: 38 μm). After the above-mentioned coating film is laminated four times, the release film is removed, and a coating film having a thickness of 20 μm is formed using the same material as the above-mentioned support sheet (1). This coating film was laminated on both surfaces of the previously prepared 80 μm coating film to form a support sheet (5) with a total thickness of 120 μm.

Support sheet (6): A solution prepared by dissolving 250 parts by mass of the acrylic resin ((a) -2) and 50.27 parts by mass of the crosslinking agent ((f) -1) in 175.13 parts of toluene, and preparing the solution in The thickness of the coating film was applied to a light release sheet (product name "SP-PET38 1031" (thickness: 38 µm)) manufactured by Lintec Corporation so that the thickness of the coating film was 20 μm. After the substrate was peeled off and only the coating film remained, the coating was applied. The film was used as a support sheet (6) with a thickness of 20 μm.

Support sheet (7): a light release sheet (product name "SP-PET75 1031", thickness 75 μm) manufactured by Lintec.

Support sheet (8): a light release sheet (product name "SP-PET100 1031", thickness 100 μm) manufactured by Lintec.

<Evaluation of support film>

Each support sheet obtained above was cut out as a test piece with a rectangular shape having a width of 15.0 mm and a length of about 150 mm.

The Young's coefficient was measured using a universal testing machine (manufactured by Shimadzu Corporation: Autograph AG-IS 500N), referring to JIS K7127: 1999, with 100 mm between fixtures and 200 mm / min tensile speed.

<Manufacture of film-shaped adhesive compound sheet>

[Example 1]

(Manufacture of adhesive composition)

Polymer component (a) -1 (10.30 parts by mass), epoxy resin (b1) -1 (26.46 parts by mass), epoxy resin (b1) -3 (16.45 parts by mass), and thermosetting agent (b2)- 1 (36.21 parts by mass), hardening accelerator (c) -1 (0.22 parts by mass), filler (d) -1 (9.36 parts by mass), and silane coupling agent (e) -1 (1.00 parts by mass) are dissolved or dispersed By stirring in methyl ethyl ketone at 23 ° C., an adhesive composition having a solid content concentration of 60% by mass was obtained as an adhesive composition.

(Manufacture of film-like adhesive composite sheet)

Apply the adhesive composition obtained above to the release-treated side of a release film ("SP-PET38 1031" manufactured by Lintec Corporation, having a thickness of 38 μm) on one side of a polyethylene terephthalate film. After drying at 110 ° C for 3 minutes, a film-shaped adhesive having a thickness of 10 µm was formed. Then, a single surface of the support sheet (1) (thickness: 38 μm) was bonded to the exposed surface of the film-shaped adhesive to obtain a film-shaped adhesive composite sheet.

[Example 2]

The support sheet (1) used in Example 1 was replaced with a support sheet (2), and the side of the glossy surface of the support sheet (2) was bonded to the exposed surface of the film-shaped adhesive. 1 The same method was used to produce a film-like adhesive composite sheet.

[Example 3]

The support sheet (1) used in Example 1 was replaced with the support sheet (3), and the side of the release-treated surface of the support sheet (3) was bonded to the exposed surface of the film-shaped adhesive. A film-like adhesive composite sheet was produced in the same manner as in Example 1.

[Example 4]

The support sheet (3) used in Example 3 was replaced with a support sheet (4). Except for this point, a film-like adhesive composite sheet was produced by the same method as in Example 3.

[Comparative Example 1]

The support sheet (1) used in Example 1 was replaced with the support sheet (5), and the single side of the support sheet (5) was bonded to the exposed surface of the film-shaped adhesive. In the same manner, a film-like adhesive composite sheet was produced.

[Comparative Example 2]

The support sheet (1) used in Example 1 was replaced with a support sheet (6), and the single side of the support sheet (6) was bonded to the exposed surface of the film-shaped adhesive. In the same manner, a film-like adhesive composite sheet was produced.

[Comparative Example 3]

The support sheet (3) used in Example 3 was replaced with a support sheet (7). Except for this point, a film-like adhesive composite sheet was produced by the same method as in Example 3.

[Comparative Example 4]

The support sheet (3) used in Example 3 was replaced with a support sheet (8). Except for this point, a film-like adhesive composite sheet was produced by the same method as in Example 3.

<Evaluation of film-shaped adhesive compound sheet>

The following items were evaluated about the film-like adhesive composite sheets of each of the examples and comparative examples obtained above.

(Evaluation of the pick-up suitability using the pin top)

The 8-inch silicon wafer was singulated into 2 mm × 2 mm wafers with a thickness of 50 μm. Next, using a laminator, the film-shaped adhesive of the film-shaped adhesive composite sheet was heated to 60 ° C., and the heated film-shaped adhesive was bonded to the dry polishing surface of the wafer. By the above operation, a test sheet in which a film-shaped adhesive compound sheet was attached to a plurality of silicon wafers was obtained.

Next, for this test piece, a pick-up device ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.) was used, under the conditions of a jacking amount of 300 μm, a jacking speed of 20 mm / min, and a lifting waiting time of 1 s. The top mode makes 27 picks. Then, it was judged that the picking suitability was good when it was successfully picked up more than 26 times, and it was judged that it was poor in picking suitability in other cases. The results are shown in Table 1.

(Measurement of elongation at break (C))

Using a laminator, heat two sheets of film-shaped adhesive (thickness: 20 μm) at 60 ° C. and stick them together. Then apply the same film-shaped adhesive similarly. Repeat the above operation to make a film thickness of 200 μm. Laminated body made of layers.

Then, using a heating plate heated to 80 ° C., the obtained laminated body was heated for 30 seconds. Then, using a super cutting machine ("PH1-600" manufactured by Takino Seiki Seisakusho), the heated laminated body was cut out within 10 seconds to produce test pieces having a width of 15 mm, a length of 100 mm, and a thickness of 200 μm. When the cutting time exceeds 10 seconds, the cutting is temporarily suspended, and a heating plate heated to 80 ° C is used to cut the laminated body within 10 seconds while heating the cutting body again to produce a test piece. The reason why the laminated body is cut after heating in this way is that the end portion of the test piece does not generate a defect portion that causes breakage.

Then, the elongation at break of the obtained test piece was measured in accordance with JIS K7161-1994. More specifically, it is as follows.

That is, a universal testing machine ("Autograph AG-IS 500N" manufactured by Shimadzu Corporation) was used, and the aforementioned test piece was fixed at two places by the fixing jig of the universal testing machine. At this time, the distance between the tip portions of the fixing jig (the length of the exposed portion of the test piece and the distance between the fixed portions) was set to 75 mm.

Next, the tensile speed was set to 200 mm / min, and the test piece was stretched between the fixed portions, and the elongation at break of the test piece was determined as the elongation at break (C) (%).

The film-like adhesives used in Examples 1 to 4 and Comparative Examples 1 to 4 all had the same elongation at break (C), which was 900%.

(Measurement of breaking strength (D))

When the elongation at break (C) is measured, the tensile stress at which the test piece is broken (broken), that is, the tensile breaking stress is measured, and the measured value is taken as the breaking strength (D) (MPa).

The breaking strength (D) of the film adhesives used in Examples 1 to 4 and Comparative Examples 1 to 4 were all the same and were 0.5 MPa.

(Measurement of adhesion (E) between film adhesive and semiconductor wafer)

The film-shaped adhesive composite sheet was cut into a size of 24 mm × 300 mm, the film-shaped adhesive was heated to 60 ° C., and the film-shaped adhesive was attached with a celluloid tape (“Cellotape (registered trademark) No. 405 ", width 24mm). Then, the substrate was peeled from the film-shaped adhesive, and the exposed film-shaped adhesive was heated to 60 ° C, and the dry polishing surface of a 6-inch silicon wafer (thickness: 350 μm) was attached while maintaining the state, thereby obtaining The laminated body of the celluloid tape, the film adhesive and the silicon wafer was used as a test piece.

The obtained laminated body was immediately left in an environment of 23 ° C. and a relative humidity of 50% (under a standard environment prescribed by JIS Z0237 2009) for 30 minutes, and then subjected to so-called 180 ° peeling, that is, using a film adhesive and silicon crystals. Laminated sheets formed by laminating film adhesives and cellophane tapes from a silicon wafer at a peeling speed of 150 mm / min so that the contact surfaces of the circles are at an angle of 180 ° with each other, and measure the peeling force at this time. This measured value was made into the adhesive force E (N / 24mm) of a film adhesive and a semiconductor wafer.

The film-like adhesive used in Examples 1 to 4 and Comparative Examples 1 to 4 and the adhesive force (E) of the semiconductor wafer were all the same, and were 10 N / 24 mm.

In addition, when E / (C × D) was obtained from these measurement results, it was 0.022 (N / 24mm / (%. MPa)).

The above results indicate that the product of the Young's coefficient (A) (MPa) and the thickness (B) (mm) of the support sheet of the film-like adhesive composite sheet of Examples 1 to 4 is (A × B) At 4MPa. mm to 150MPa. In the range of mm, for the silicon wafer to which the film-shaped adhesives of these sheets are attached, the single-pin top-up method can be used even if the main purpose of cutting the film-shaped adhesive is not separately provided. The film-like adhesive is cut while suppressing the occurrence of step abnormalities. In addition, the silicon wafer to which the cut-off film-shaped adhesive is attached can be separated from the support sheet while suppressing the occurrence of step abnormalities. In this way, the film-like adhesive composite sheets of Examples 1 to 4 exhibited good picking suitability in the single-pin top-up method.

In contrast, the product (A × B) of the Young's coefficient (A) (MPa) and the thickness (B) (mm) of the support sheet of the film-like adhesive composite sheet of Comparative Examples 1 to 4 is less than 4MPa. mm or more than 150MPa. mm, does not satisfy the aforementioned range. In addition, the silicon wafer to which the film-shaped adhesive on these sheets are attached has a large number of abnormalities in the period from the cutting of the film-shaped adhesive to the separation of the silicon wafer with the film-shaped adhesive from the support sheet. Poor adaptability.

(Industrial availability)

Since the present invention can be used for manufacturing a semiconductor device, it is extremely useful in industry.

Claims (3)

    A film-shaped adhesive composite sheet is provided on a supporting sheet with a hardening film-shaped adhesive; the supporting sheet has a substrate; the thickness of the hardening film-shaped adhesive is 1 μm to 60 μm; and the Young's coefficient of the supporting sheet And the product of the thickness of the aforementioned support sheet is 4 MPa. mm to 150MPa. mm.         The film-shaped adhesive composite sheet according to claim 1, wherein the film-shaped adhesive has the following characteristics: when the film-shaped adhesive before curing is laminated to form a laminated body having a total thickness of 200 μm, the laminated body The elongation at break becomes 1% to 2000%.         A method for manufacturing a semiconductor device, comprising using the film-like adhesive composite sheet according to claim 1, and including attaching the film-like adhesive composite sheet to a plurality of divided pieces through the film-like adhesive. Semiconductor wafer; for the support sheet in the film-shaped adhesive composite sheet attached to the semiconductor wafer, the film-shaped adhesive is interposed from the side opposite to the side on which the film-shaped adhesive is provided via the support sheet. By applying force, the film-shaped adhesive is cut; and the semiconductor wafer and the film-shaped adhesive adhered to the semiconductor wafer are separated from the support sheet.