阅读说明：本技术 半导体装置的制造方法、晶粒接合膜及切割晶粒接合一体型粘合片 (Method for manufacturing semiconductor device, die bonding film, and dicing die bonding integrated adhesive sheet ) 是由 上田麻未 谷口纮平 于 2020-03-13 设计创作，主要内容包括：本发明公开了一种用于将半导体晶片与搭载所述半导体晶片的支承部件粘合的晶粒接合膜。该晶粒接合膜在-15℃下的断裂伸长率为5％以下。另外,该晶粒接合膜包含环氧树脂、环氧树脂固化剂、及含有环氧基的(甲基)丙烯酸共聚物,以环氧树脂、环氧树脂固化剂及含有环氧基的(甲基)丙烯酸共聚物的总量为基准,环氧树脂及环氧树脂固化剂的合计含量为10质量％以上且小于30质量％。晶粒接合膜在-15℃下的断裂伸长率为5％以下。(The invention discloses a die bonding film for bonding a semiconductor wafer to a support member on which the semiconductor wafer is mounted. The grain bonding film has an elongation at break of 5% or less at-15 ℃. The die bond film contains an epoxy resin, an epoxy resin curing agent, and an epoxy group-containing (meth) acrylic copolymer, and the total content of the epoxy resin and the epoxy resin curing agent is 10 mass% or more and less than 30 mass%, based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer. The grain-bonding film has an elongation at break of 5% or less at-15 ℃.)

1. A method of manufacturing a semiconductor device, comprising:

a step of preparing a dicing die-bonding integrated adhesive sheet, the dicing die-bonding integrated adhesive sheet comprising in order: an adhesive layer, a pressure-sensitive adhesive layer, and a base material film, each of which is composed of a grain-bonded film having an elongation at break at-15 ℃ of 5% or less;

preparing a semiconductor wafer and forming a modified layer on the semiconductor wafer;

a step of attaching the surface of the adhesive layer of the dicing die-bond integrated adhesive sheet to a semiconductor wafer;

a step of producing a semiconductor chip with an adhesive layer by expanding the base film to singulate the semiconductor wafer and the adhesive layer;

picking up the semiconductor wafer with the adhesive layer from the pressure-sensitive adhesive layer; and

a step of bonding the semiconductor wafer with the adhesive layer to a support substrate for mounting a semiconductor wafer via the adhesive layer; and is

The die-bonding film includes: an epoxy resin, an epoxy resin curing agent, and an epoxy group-containing (meth) acrylic copolymer,

the total content of the epoxy resin and the epoxy resin curing agent is 10 mass% or more and less than 30 mass% based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer.

2. The method for manufacturing a semiconductor device according to claim 1,

the die bond film has a die shear strength of 0.7MPa or more at 250 ℃ in a cured product of the die bond film obtained by thermally pressing the die bond film onto a wiring board and curing the die bond film at 170 ℃ for 3 hours.

3. The method for manufacturing a semiconductor device according to claim 1 or 2,

the die-bonding film further comprises a silane coupling agent.

4. The method for manufacturing a semiconductor device according to claim 3,

the silane coupling agent is a silane coupling agent represented by the following general formula (1),

in the general formula (1), R is alkoxy, and n is an integer of 1-3.

5. The method for manufacturing a semiconductor device according to any one of claims 1 to 4,

the die-bond film also contains an inorganic filler,

the content of the inorganic filler is 25 mass% or more based on the total amount of the grain-bonded film.

6. The method for manufacturing a semiconductor device according to any one of claims 1 to 5,

the content of the epoxy group-containing (meth) acrylic copolymer is 60% by mass or less based on the total amount of the die bond film.

7. A die bond film for bonding a semiconductor wafer to a supporting member on which the semiconductor wafer is mounted,

the grain bonding film has an elongation at break of 5% or less at-15 ℃, and

the die-bonding film comprises an epoxy resin, an epoxy resin curing agent, and an epoxy group-containing (meth) acrylic copolymer,

the total content of the epoxy resin and the epoxy resin curing agent is 10 mass% or more and less than 30 mass% based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer.

8. The die-bonding film according to claim 7,

the die bond film has a die shear strength of 0.7MPa or more at 250 ℃ in a cured product of the die bond film obtained by thermally pressing the die bond film onto a wiring board and curing the die bond film at 170 ℃ for 3 hours.

9. The die-bonding film according to claim 7 or 8,

the die-bonding film further comprises a silane coupling agent.

10. The die-bonding film of claim 9, wherein,

the silane coupling agent is a silane coupling agent represented by the following general formula (1),

in the general formula (1), R is alkoxy, and n is an integer of 1-3.

11. The die-bonding film according to any one of claims 7 to 10, further comprising an inorganic filler, wherein,

the content of the inorganic filler is 25 mass% or more based on the total amount of the grain-bonded film.

12. The die-bonding film according to any one of claims 7 to 11,

the content of the epoxy group-containing (meth) acrylic copolymer is 60% by mass or less based on the total amount of the die bond film.

13. A dicing die-bonding integrated adhesive sheet comprising, in order:

an adhesive layer consisting of the die-bonding film according to any one of claims 7 to 12;

a pressure sensitive adhesive layer; and

a substrate film.

Technical Field

The present invention relates to a method for manufacturing a semiconductor device, a die-bonding film, and a dicing die-bonding (dicing/die-bonding) integrated adhesive sheet.

Background

As a method for manufacturing a semiconductor device, a back-surface-mount method of a semiconductor wafer is generally used. The back surface attaching method of the semiconductor wafer is as follows: a die bond film and a dicing tape are attached to the back surface of a semiconductor wafer, and then the semiconductor wafer, the die bond film and a part of the dicing tape are cut in a dicing step. For example, a method of attaching a die bonding film to a dicing tape and attaching the die bonding film to a semiconductor wafer has been proposed (for example, see patent documents 1 to 4).

However, in recent years, in order to increase the storage capacity per package, the number of stacked wafers in the package is increasing. Accordingly, it has been studied to make the thickness of a semiconductor wafer thinner by a back grinding process or the like, and to manufacture a semiconductor wafer having a thickness of, for example, 30 μm or less. When the semiconductor wafer is made thin, the semiconductor wafer is likely to be broken in the dicing step, and thus the manufacturing efficiency may be significantly reduced.

As a method for singulating a relatively thin semiconductor wafer, for example, the following methods (stealth dicing) are known: the inside of the semiconductor wafer on the planned cutting line is irradiated with laser light to form a modified layer, and then the outer peripheral portion is expanded to singulate the semiconductor wafer (see, for example, patent document 5). In stealth dicing, even when the thickness of a semiconductor wafer is relatively thin, it is effective to reduce defects such as chipping (chipping), and thus improvement in manufacturing efficiency can be expected.

As a dicing die-bonding integrated adhesive sheet used for such stealth dicing, an expandable semiconductor wafer processing tape used when an adhesive layer is divided along a wafer by expansion is disclosed (for example, refer to patent document 6).

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2002-226796

Patent document 2: japanese patent laid-open No. 2002-158276

Patent document 3: japanese patent laid-open No. Hei 02-032181

Patent document 4: international publication No. 04/109786

Patent document 5: japanese patent laid-open No. 2003-338467

Patent document 6: japanese patent laid-open publication No. 2011-216508

Disclosure of Invention

Technical problem to be solved by the invention

However, the die bond film in the dicing die-bond integrated type adhesive sheet is generally flexible and stretchable, and therefore, when the base material film is expanded, there is a problem that the die bond film is difficult to be divided.

Means for solving the technical problem

Accordingly, a main object of the present invention is to provide a die bond film having excellent cuttability and a method for manufacturing a semiconductor device using the die bond film.

Conventionally, it is known that in order to improve the cuttability of a dicing die-bond integrated adhesive sheet, an increase in stress due to thermal shrinkage of a base film of a dicing tape is adjusted (for example, refer to patent document 6). Under such circumstances, the present inventors have conducted extensive studies and as a result, have found that the elongation at break of the grain junction film affects the cuttability, and have completed the present invention.

One aspect of the present invention relates to a method of manufacturing a semiconductor device. The method for manufacturing the semiconductor device comprises the following steps: a step of preparing a dicing die-bonding integrated adhesive sheet, the dicing die-bonding integrated adhesive sheet comprising in order: an adhesive layer, a pressure-sensitive adhesive layer, and a base material film, each of which is composed of a grain-bonded film having an elongation at break at-15 ℃ of 5% or less; preparing a semiconductor wafer and forming a modified layer on the semiconductor wafer; a step of attaching the surface of the adhesive layer of the dicing die-bond integrated adhesive sheet to a semiconductor wafer; a step of producing a semiconductor chip with an adhesive layer by expanding the base film to singulate the semiconductor wafer and the adhesive layer; picking up the semiconductor wafer with the adhesive layer from the pressure-sensitive adhesive layer; and a step of bonding the semiconductor wafer with the adhesive layer to the support substrate for mounting a semiconductor wafer via the adhesive layer. The die bond film includes: the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer are contained in a total amount of 10 mass% or more and less than 30 mass%, based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer.

Regarding the die bond film, the die bond film may have a 250 ℃ die shear strength of 0.7MPa or more in a cured product of the die bond film obtained by thermally pressing the die bond film on a wiring board and curing the film at 170 ℃ for 3 hours.

The die-bonding film may further include a silane coupling agent.

The silane coupling agent may be a silane coupling agent represented by the following general formula (1).

[ in the general formula (1), R is alkoxy, and n is an integer of 1 to 3 ].

The die-bond film may also contain an inorganic filler. The content of the inorganic filler may be 25 mass% or more based on the total amount of the grain-bonded film.

The content of the epoxy group-containing (meth) acrylic copolymer may be 60% by mass or less based on the total amount of the die bond film.

Another aspect of the present invention relates to a die bond film for bonding a semiconductor wafer and a support member on which the semiconductor wafer is mounted. The grain bonding film has an elongation at break of 5% or less at-15 ℃. The die bond film contains an epoxy resin, an epoxy resin curing agent, and an epoxy group-containing (meth) acrylic copolymer, and the total content of the epoxy resin and the epoxy resin curing agent is 10 mass% or more and less than 30 mass% based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer.

Another aspect of the present invention relates to a dicing die-bonding integrated type adhesive sheet. The dicing die-bonding integrated adhesive sheet comprises in order: an adhesive layer, a pressure-sensitive adhesive layer, and a base film, each of which is composed of the above-described die bond film.

Effects of the invention

According to the present invention, a die bond film having excellent cuttability and a method for manufacturing a semiconductor device using the die bond film are provided. The die bond films of several types are excellent in both the die shear strength and embeddability. Further, the present invention provides a dicing die-bonding integrated adhesive sheet using such a die-bonding film.

Drawings

Fig. 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device.

Fig. 2 is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a semiconductor device, and (a), (b), (c), (d), and (e) of fig. 2 are schematic cross-sectional views showing respective steps.

Fig. 3 is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a semiconductor device, and (f), (g), (h), and (i) of fig. 3 are schematic cross-sectional views showing respective steps.

Fig. 4 is a schematic cross-sectional view showing an embodiment of a dicing die-bonding integrated adhesive sheet.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the steps) are not essential unless otherwise noted. The sizes of the components in the drawings are conceptual sizes, and the relative relationship between the sizes of the components is not limited to the relationship shown in the drawings.

The numerical values and ranges thereof in the present specification are also equivalent and do not limit the present invention. In the present specification, a numerical range represented by "to" represents a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively. In the numerical ranges recited in the present specification in stages, the upper limit value or the lower limit value recited in one numerical range may be replaced with the upper limit value or the lower limit value recited in another numerical range recited in stages. In addition, in the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

In the present specification, (meth) acrylate means acrylate or methacrylate corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl group and (meth) acrylic acid copolymer.

[ semiconductor device ]

Fig. 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device. In the semiconductor device 100 shown in fig. 1, the semiconductor wafer Wa is bonded to the semiconductor wafer mounting support substrate 60 via the adhesive layer 30a (or a cured product of the adhesive layer 30 a). The semiconductor wafer Wa is electrically connected to the support substrate 60 for mounting a semiconductor wafer by bonding wires 70. The semiconductor wafer Wa is resin-sealed on the surface 60a of the support substrate 60 for mounting a semiconductor wafer by a resin sealing material 80. Solder balls 90 are formed on the surface of the support substrate 60 for mounting a semiconductor wafer, the surface being opposite to the front surface 60a, and the solder balls are electrically connected to an external substrate (motherboard).

As the semiconductor wafer, for example, a general semiconductor wafer such as IC, LSI, VLSI, or the like can be used.

As the supporting substrate for mounting a semiconductor chip, for example, a lead frame having a die pad, a ceramic substrate, an organic substrate, or the like can be used, and the supporting substrate is not limited to a substrate material. Examples of the ceramic substrate include an alumina substrate and an aluminum nitride substrate. Examples of the organic substrate include an FR-4 substrate in which a glass cloth is impregnated with an epoxy resin, a BT substrate in which a bismaleimide-triazine resin is impregnated, and a polyimide film substrate in which a polyimide film is used as a base material.

The wiring provided on the support substrate for mounting a semiconductor wafer may be any of single-sided wiring, double-sided wiring, and multilayer wiring, and if necessary, a through hole or a non-through hole electrically connected to the support substrate for mounting a semiconductor wafer may be provided. Further, when the wiring is arranged outside the semiconductor device, a protective resin layer may be provided.

[ method for manufacturing semiconductor device (semiconductor Package) ]

Fig. 2 (a) to (e) and fig. 3 (f) to (i) are schematic cross-sectional views for explaining an embodiment of a method for manufacturing a semiconductor device. The method for manufacturing a semiconductor device according to one embodiment includes: a step of preparing a dicing die-bonding integrated adhesive sheet (dicing die-bonding integrated adhesive sheet preparation step) which sequentially comprises: an adhesive layer, a pressure-sensitive adhesive layer, and a base material film, each of which is composed of a grain-bonded film having an elongation at break at-15 ℃ of 5% or less; a step of preparing a semiconductor wafer and forming a modified layer on the semiconductor wafer (modified layer forming step); a step (wafer laminating step) of attaching the surface of the adhesive layer of the dicing die-bond integrated adhesive sheet to a semiconductor wafer; a step (dicing step) of producing a semiconductor chip with an adhesive layer by expanding the base film to singulate the semiconductor wafer and the adhesive layer; a step (pickup step) of picking up the semiconductor wafer with the adhesive layer from the pressure-sensitive adhesive layer; and a step (semiconductor wafer bonding step) of bonding the semiconductor wafer with the adhesive layer to the support substrate via the adhesive layer.

< preparation Process of dicing die-bonding Integrated adhesive sheet >

Fig. 4 is a schematic cross-sectional view showing an embodiment of a dicing die-bonding integrated adhesive sheet. The dicing die-bond integrated adhesive sheet 1 includes an adhesive layer 30, a pressure-sensitive adhesive layer 20, and a base film 10 in this order.

(adhesive layer)

The die bond film constituting the adhesive layer 30 is thermosetting and can be in a completely cured (C-stage) state after being subjected to a semi-curing (B-stage) state and a curing treatment.

The grain-bonding film has an elongation at break of 5% or less at-15 ℃. By using such a die bond film, the die bond film tends to be easily cleaved during expansion. The elongation at break of the grain-bonded film at-15 ℃ may be 4.5% or less, 4% or less, or 3.5% or less. The elongation at break of the grain-bonded film at-15 ℃ may be 0.5% or more, for example. In the present specification, the elongation at break at-15 ℃ is a value measured by the method described in examples.

The die bond film includes: an epoxy resin (hereinafter, sometimes referred to as "component (a)"), an epoxy resin curing agent (hereinafter, sometimes referred to as "component (B)"), and an epoxy group-containing (meth) acrylic copolymer (hereinafter, sometimes referred to as "component (C)"). The grain-bonding film may further contain an inorganic filler (hereinafter, sometimes referred to as "component (D)") and a silane coupling agent (hereinafter, sometimes referred to as "component (E)"). By adjusting the kind and content of these components, the breaking elongation of the die bond film at-15 ℃ can be adjusted.

(A) The components: epoxy resin

(A) The component (b) is a component which has a property of forming a three-dimensional bond between molecules by heating or the like and curing, and exhibits an adhesive effect after curing. (A) The component (c) may be used without any particular limitation as long as it has an epoxy group in the molecule. (A) The component (c) may have two or more epoxy groups in the molecule.

Examples of the component (a) include: bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol a novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, stilbene-type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, trisphenol methane-type epoxy resins, biphenyl-type epoxy resins, xylylene-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracenes, and the like. These may be used alone or in combination of two or more. Among them, the component (a) may be a cresol novolak type epoxy resin, a bisphenol type epoxy resin, or a dicyclopentadiene type epoxy resin from the viewpoint of the tackiness, flexibility, and the like of the film.

(A) The epoxy equivalent of the component (A) is not particularly limited, and may be 90 to 300g/eq, 110 to 290g/eq, or 130 to 280 g/eq. When the epoxy equivalent of the component (a) is within this range, the elongation at break of the die bond film tends to be lower. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded.

The content of the component (A) may be 1 to 30% by mass based on the total amount of the grain bonding film. When the content of the component (a) is 1 mass% or more based on the total amount of the crystal grain bonding film, the degree of crosslinking of the film increases, the overall strength increases, and peeling from the substrate tends to be difficult, and when the content is 30 mass% or less, the heat resistance history and the storage stability of the film tend to be improved. The content of the component (a) may be 2 mass% or more, 3 mass% or more, or 5 mass% or more, or 20 mass% or less, 15 mass% or less, or 10 mass% or less based on the total amount of the grain bonding film.

(B) The components: epoxy resin curing agent

(B) The component (c) may be, for example, a phenol resin which can be a curing agent for an epoxy resin. The phenol resin is not particularly limited as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenolic resin include: phenol novolac-type phenol resins obtained by condensation or co-condensation of phenols such as phenol, cresol, resorcinol, catechol, bisphenol a, bisphenol F, phenylphenol, and aminophenol and/or naphthols such as α -naphthol, β -naphthol, and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde under an acidic catalyst, phenol aralkyl resins synthesized from phenols such as allylated bisphenol a, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenols such as phenol and/or naphthols and dimethoxyp-xylene or bis (methoxymethyl) biphenyl, naphthol aralkyl resins, biphenyl aralkyl-type phenol resins, and phenyl aralkyl-type phenol resins. These may be used alone or in combination of two or more.

The phenolic resin may have a hydroxyl equivalent of 40 to 300g/eq, 70 to 290g/eq, or 100 to 280 g/eq. When the hydroxyl equivalent of the phenolic resin is 40g/eq or more, the storage modulus of elasticity of the film tends to be further improved, and when the hydroxyl equivalent is 300g/eq or less, problems due to foaming, degassing, and the like can be prevented.

From the viewpoint of curability, the ratio of the epoxy equivalent of the component (a) to the hydroxyl equivalent of the phenol resin ((epoxy equivalent of the component (a)/hydroxyl equivalent of the phenol resin)) may be: 0.30/0.70-0.70/0.30, 0.35/0.65-0.65/0.35, 0.40/0.60-0.60/0.40, or 0.45/0.55-0.55/0.45. When the equivalent ratio is 0.30/0.70 or more, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70/0.30 or less, the viscosity can be prevented from becoming excessively high, and more sufficient fluidity can be obtained.

The content of the component (B) may be 1 to 30% by mass based on the total amount of the grain bonding film. When the content of the component (B) is 1 mass% or more based on the total amount of the crystal grain bonding film, the degree of crosslinking of the film increases, the overall strength tends to be improved, and peeling from the substrate tends to be difficult, and when the content is 30 mass% or less, the heat resistance history and the storage stability of the film tend to be improved. The content of the component (B) may be 2 mass% or more, 3 mass% or more, or 5 mass% or more, or 20 mass% or less, 15 mass% or less, or 10 mass% or less based on the total amount of the grain bonding film.

The total content of the component (a) and the component (B) may be 25% by mass or less based on the total amount of the grain bonding film. The total content of the component (a) and the component (B) may be 20 mass% or less, 18 mass% or less, or 15 mass% or less, based on the total amount of the grain-bonding film. The total content of the component (a) and the component (B) may be 3 mass% or more, 5 mass% or more, or 7 mass% or more, based on the total amount of the grain-bonding film.

(C) The components: epoxy group-containing (meth) acrylic copolymer

The (meth) acrylic acid copolymer refers to a polymer containing a constituent unit derived from a (meth) acrylic acid ester. The epoxy group-containing (meth) acrylic copolymer is a polymer containing, as a constituent unit, a constituent unit derived from an epoxy group-containing (meth) acrylate. The (meth) acrylic copolymer may be an acrylic rubber such as a copolymer of a (meth) acrylate and acrylonitrile. These may be used alone or in combination of two or more.

Examples of commercially available products of component (C) include: "SG-70L", "SG-708-6", "WS-023 EK 30", "SG-280 EK 23", "HTR-860P-3 CSP-3 DB" (all manufactured by Nagase ChemteX Corporation).

(C) The glass transition temperature (Tg) of the component may be-50 to 50 ℃ or-30 to 20 ℃. When the Tg of the acrylic resin is-50 ℃ or higher, the adhesiveness of the crystal grain bonding film is lowered, and therefore the workability tends to be further improved. When the Tg of the acrylic resin is 50 ℃ or lower, the fluidity of the adhesive composition at the time of forming the die bond film tends to be more sufficiently ensured. The glass transition temperature (Tg) of the component (C) is a value measured by a DSC (differential scanning calorimeter) (for example, "Thermo Plus 2" manufactured by Rigaku).

(C) The weight average molecular weight (Mw) of the component (B) may be 5 to 120 ten thousand, 10 to 120 ten thousand, or 30 to 90 ten thousand. (C) When the weight average molecular weight of the component (a) is 5 ten thousand or more, the film-forming property tends to be more excellent. (C) When the weight average molecular weight of the component (b) is 120 ten thousand or less, the fluidity of the adhesive composition tends to be more excellent when a grain-bonding film is formed. The weight average molecular weight (Mw) is a value measured by Gel Permeation Chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

(C) The measurement apparatus and measurement conditions for the weight average molecular weight (Mw) of the component are as follows.

A pump: l-6000(Hitachi, manufactured by Ltd.)

Pipe column: a column comprising a string of 10.7mm (diameter). times.300 mm each comprising Gilpak (Gelpack) GL-R440 (manufactured by Hitachi Chemical Company, Ltd.), Gilpak (Gelpack) GL-R450 (manufactured by Hitachi Chemical Company, Ltd.), and Gilpak GL-R400M (manufactured by Hitachi Chemical Company, Ltd.) connected in this order

And (3) dissolving and separating liquid: tetrahydrofuran (hereinafter referred to as "THF")

Sample preparation: 120mg of sample was dissolved in THF5mL

Flow rate: 1.75 mL/min

The total content of the component (A) and the component (B) is 10 mass% or more and less than 30 mass% based on the total amount of the component (A), the component (B) and the component (C). When the total content of the component (a) and the component (B) is less than 30% by mass based on the total amount of the component (a), the component (B), and the component (C), the elongation at break of the grain-bonded film tends to be low. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. When the total content of the component (a) and the component (B) is 10 mass% or more based on the total amount of the component (a), the component (B), and the component (C), a cured product of the die bond film obtained by thermally bonding the die bond film to the wiring board and curing the die bond film at 170 ℃ for 3 hours tends to exhibit higher die shear strength. The total content of the component (a) and the component (B) may be 28 mass% or less, 25 mass% or less, 22 mass% or less, or 20 mass% or less, or may be 12 mass% or more, or 15 mass% or more, based on the total amount of the component (a), the component (B), and the component (C).

The content of the component (C) may be more than 70% by mass and 90% by mass or less based on the total amount of the component (a), the component (B) and the component (C). When the content of component (C) exceeds 70% by mass based on the total amount of component (A), component (B) and component (C), the orientation is as follows: the step of the substrate when the die bond film is thermally pressed against the wiring substrate and molded is easily embedded. When the content of the component (C) is 90 mass% or less based on the total amount of the component (a), the component (B) and the component (C), the elongation at break of the grain-bonded film tends to be low. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. The content of the component (C) may be 72 mass% or more, 75 mass% or more, 78 mass% or more, or 80 mass% or more, or 88 mass% or less, or 85 mass% or less, based on the total amount of the component (a), the component (B), and the component (C).

The content of the component (C) may be 60 mass% or less based on the total amount of the grain-bonding film. When the content of the component (C) is 60 mass% or less based on the total amount of the grain bonding film, the elongation at break of the grain bonding film tends to be lower. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. The content of the component (C) may be 58 mass% or less based on the total amount of the grain-bonding film. The content of the component (C) may be 35 mass% or more, 40 mass% or more, or 45 mass% or more based on the total amount of the grain bonding film.

(D) The components: inorganic filler

Examples of the component (D) include: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and the like. These may be used alone or in combination of two or more. Of these, the component (D) may be silica.

If the average particle diameter ratio of the component (D) is large, the breaking elongation of the die bond film tends to be low. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. (D) The average particle diameter of the component (A) may be 0.1 to 1.0. mu.m. (D) The average particle diameter of the component (A) may be 0.2 to 0.3 μm, or 0.4 μm, or 0.9 to 0.8 μm, or 0.7 μm. The average particle diameter is a value obtained by converting the BET specific surface area.

(D) The shape of the component may be spherical. The spherical shape is a concept including a regular spherical shape.

The component (D) may be surface-treated with a surface-treating agent from the viewpoint of compatibility and adhesive strength between the surface of the component (D) and a solvent, other components, and the like. Examples of the surface treatment agent include silane coupling agents. Examples of the functional group of the silane coupling agent include a vinyl group, a (meth) acryloyl group, an epoxy group, a mercapto group, an amino group, a diamino group, an alkoxy group, and an ethoxy group.

The content of the component (D) may be 25% by mass or more based on the total amount of the grain-bonding film. When the content of the component (D) is 25 mass% or more based on the total amount of the grain bonding film, the elongation at break of the grain bonding film tends to be further reduced. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. The content of the component (D) may be 26 mass% or more or 28 mass% or more based on the total amount of the grain-bonding film. The content of the component (D) may be 50 mass% or less, 45 mass% or less, or 40 mass% or less based on the total amount of the grain-bonding film. When the die bond film contains the component (D), the total content of the component (a), the component (B), and the component (C) may be 75 mass% or less, 74 mass% or less, or 72 mass% or less, or 50 mass% or more, 55 mass% or more, or 60 mass% or more, based on the total amount of the die bond film.

(D) The mass ratio of component (C) to component (D), (the mass of component (D)/the mass of component (C)) may be 0.30 or more, 0.35 or more, 0.40 or more, 0.45 or more, or 0.50 or more. (D) When the mass ratio of component (C) to component (D), (the mass of component (D)/the mass of component (C)) is 0.30 or more, the elongation at break of the grain junction film tends to be low. As a result, the finally obtained die bond film tends to be more likely to concentrate stress and to be easily divided when expanded. (D) The mass ratio of component (D) to component (C), (the mass of component (D)/(the mass of component (C)) may be, for example, 0.80 or less, 0.70 or less, or 0.60 or less.

(E) The components: silane coupling agent

The grain-bonding film contains the component (E), and thus the interfacial bonding between the different components tends to be further improved. (E) The component (b) may be a silane coupling agent represented by the following general formula (1).

In the general formula (1), R is alkoxy such as methoxy, ethoxy and the like, and n is an integer of 1 to 3.

Examples of the silane coupling agent represented by the general formula (1) include: phenylaminopropyltrimethoxysilane, phenylaminopropyltriethoxysilane, phenylaminoethyltrimethoxysilane, phenylaminoethyltriethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, etc.

(E) The component (C) may contain a silane coupling agent other than the silane coupling agent represented by the general formula (1). Examples of such a silane coupling agent include: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (N, N-dimethyl) aminopropyltrimethoxysilane, gamma- (N, N-diethyl) aminopropyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-butyltrimethoxysilane, or-butyltrimethoxysilane, gamma-butyltrimethoxysilane, or-butyltrimethoxysilane, Gamma- (N, N-dibutyl) aminopropyltrimethoxysilane, gamma- (N-methyl) phenylaminopropyltrimethoxysilane, gamma- (N-ethyl) phenylaminopropyltrimethoxysilane, gamma- (N, N-dimethyl) aminopropyltriethoxysilane, gamma- (N, N-diethyl) aminopropyltriethoxysilane, gamma- (N, N-dibutyl) aminopropyltriethoxysilane, gamma- (N-methyl) phenylaminopropyltriethoxysilane, gamma- (N, N-dimethyl) aminopropylmethyldimethoxysilane, gamma- (N, N-diethyl) aminopropylmethyldimethoxysilane, gamma- (N, N-dibutyl) aminopropylmethyldimethoxysilane, n-dibutyl) aminopropylmethyldimethoxysilane, gamma- (N-methyl) phenylaminopropylmethyldimethoxysilane, gamma- (N-ethyl) phenylaminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, gamma-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane, etc. These may be used alone or in combination of two or more.

The content of the component (E) may be 0.01 to 3.0 mass% based on the total amount of the grain bonding film. (E) When the content of the component is within such a range, interfacial bonding between different components tends to be further improved.

The mass ratio of the silane coupling agent represented by general formula (1) to the total amount of the component (E) (mass of the silane coupling agent represented by general formula (1/(total mass of the component (E)) may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.85 or more.

The die-bonding film may further contain a curing accelerator (hereinafter, sometimes referred to as "F component").

(F) The components: curing accelerator

The die bond film contains the component (F), and thus the adhesion and the process time tend to be compatible. Examples of the component (F) include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like. These may be used alone or in combination of two or more. Among these, the component (F) may be an imidazole and a derivative thereof from the viewpoint of reactivity.

Examples of imidazoles include: 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, and the like. These may be used alone or in combination of two or more.

The content of the component (F) may be 0.001 to 1% by mass based on the total amount of the grain bonding film. (F) When the content of the component (b) is within such a range, the storage stability tends to be improved while achieving both the adhesiveness and the reduction in the process time.

Other ingredients

The die-bonding film may further contain an antioxidant, a rheology control agent, a leveling agent, and the like as other components. The content of these components may be 0.01 to 3% by mass based on the total amount of the grain-bonding film.

The die bond film can be produced by forming a pressure-sensitive adhesive composition containing the components (a) to (C) and, if necessary, the components (D) to (F) and other components into a film. Such a grain-bonding film can be formed by coating an adhesive composition on a support film. The adhesive composition may be used as a varnish of an adhesive composition diluted with a solvent. In the case of using the varnish of the adhesive composition, the die-bonding film can be formed by coating the varnish of the adhesive composition on the support film, and removing the solvent by heating and drying.

The solvent is not particularly limited as long as it can dissolve components other than the component (D). Examples of the solvent include: aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1, 4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ -butyrolactone, and the like; carbonates such as ethylene carbonate and propylene carbonate; amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone from the viewpoint of solubility and boiling point. The solid content concentration in the varnish of the adhesive composition may be 10 to 80% by mass based on the total mass of the varnish of the adhesive composition.

The varnish of the pressure-sensitive adhesive composition can be prepared by mixing and kneading the components (a) to (C) and, if necessary, the components (D) to (F), other components, and a solvent. The order of mixing and kneading the components is not particularly limited and may be appropriately set. The mixing and kneading may be carried out by appropriately combining a conventional dispersing machine such as a mixer, a kneader, a three-roll mill, a ball mill, or a bead mill. After the varnish of the adhesive composition is prepared, air bubbles in the varnish may be removed by vacuum degassing or the like.

The support film is not particularly limited, and examples thereof include: polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, and the like. The thickness of the support film may be, for example, 10 to 200 μm or 20 to 170 μm.

As a method for applying the varnish of the adhesive composition to the support film, known methods can be used, and examples thereof include: knife coating, roll coating, spray coating, gravure coating, bar coating, curtain coating, and the like. The conditions for the heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 0.1 to 90 minutes at 50 to 200 ℃.

The thickness of the die bond film can be appropriately adjusted according to the application. The thickness of the die bonding film may be 3 to 40 μm, 5 to 35 μm, or 7 to 30 μm.

Regarding the die bond film, the die bond film may have a 250 ℃ die shear strength of 0.7MPa or more in a cured product of the die bond film obtained by thermally pressing the die bond film on a wiring board and curing the film at 170 ℃ for 3 hours. When the die shear strength at 250 ℃ is 0.7MPa or more, peeling between the die bond film and the substrate during substrate transportation and mixing of foreign matter between the semiconductor wafer and the die bond film during molding can be prevented. The crystal grain shear strength at 250 ℃ may be 0.8MPa or more, 1.0MPa or more, or 1.2MPa or more. The upper limit of the grain shear strength at 250 ℃ is not particularly limited, and may be, for example, 3MPa or less.

The obtained die bond film can be used directly as the adhesive layer 30.

(pressure-sensitive adhesive layer and base film)

As the pressure-sensitive adhesive layer 20 and the base film 10, a dicing tape, which is a laminate in which the pressure-sensitive adhesive layer 20 is provided on the base film 10, can be used.

The pressure-sensitive adhesive layer 20 may be a layer cured by high-energy rays or heat (i.e., controllable adhesive force), a layer cured by high-energy rays, or a layer cured by ultraviolet rays. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may use a pressure-sensitive adhesive generally used in the field of dicing tapes. The pressure-sensitive adhesive may be suitably selected from those which have reduced adhesive force to the adhesive layer 30 by irradiation with high-energy rays.

As the substrate film 10, a substrate film generally used in the field of dicing tapes can be used. The base material of the base material film 10 is not particularly limited as long as it is expandable in the cutting step, and examples thereof include: crystalline polypropylene, amorphous polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, low-density linear polyethylene, polyolefin such as polybutene or polymethylpentene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyester such as polyethylene naphthalate, polycarbonate, polyimide, polyether ether ketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyphenylene sulfide, aramid (paper), glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose-based resin, polyethylene terephthalate, polyethylene naphthalate, etc., and the like, Silicone resins, and the like. Of these, the base material of the base material film 10 may be polypropylene, a polyethylene-polypropylene random copolymer, a polyethylene-polypropylene block copolymer, an ethylene-vinyl acetate copolymer, an ionomer resin, or an ethylene- (meth) acrylic acid copolymer, from the viewpoint of characteristics such as young's modulus, stress relaxation property, melting point, and the like.

The dicing die-bond integrated adhesive sheet 1 including the adhesive layer 30, the pressure-sensitive adhesive layer 20, and the base film 10 in this order can be obtained by bonding the die-bond film and the pressure-sensitive adhesive layer of the dicing tape.

< modified layer Forming Process >

First, a semiconductor wafer W1 having a thickness of H1 is prepared. The thickness H1 of the semiconductor wafer W1 on which the modified layer is formed may exceed 35 μm. Next, the protective film 2 is attached to one main surface of the semiconductor wafer W1 (see fig. 2 (a)). The surface to which the protective film 2 is attached may be a circuit surface of the semiconductor wafer W1. The protective film 2 may be a back grinding tape used for back grinding (back grinding) of a semiconductor wafer. Next, the inside of the semiconductor wafer W1 is irradiated with laser light to form the modified layer 4 (see fig. 2 b), and the side (back side) of the semiconductor wafer W1 opposite to the side to which the protective film 2 is attached is subjected to back grinding (back grinding) and polishing (grinding), thereby producing a semiconductor wafer W2 having the modified layer 4 (see fig. 2 c). The thickness H2 of the obtained semiconductor wafer W2 may be 35 μm or less.

< wafer lamination Process >

Next, the adhesive layer 30 of the dicing die-bond integrated adhesive sheet 1 is disposed in a predetermined apparatus. Then, the dicing die-bond integrated adhesive sheet 1 is attached to the main surface Ws of the semiconductor wafer W2 via the adhesive layer 30 (see fig. 2 (d)), and the protective film 2 of the semiconductor wafer W2 is peeled (see fig. 2 (e)).

< cutting Process >

Next, under cooling conditions, the base film 10 is expanded, whereby the semiconductor wafer W2 is divided into the modified layer 4. Thus, the semiconductor wafer W2 and the adhesive layer 30 are singulated to produce a semiconductor chip with an adhesive layer (see fig. 3 (f)). The conditions for expanding the substrate film 10 may be cooling conditions of 0 ℃ or lower.

< ultraviolet irradiation Process >

For the pressure-sensitive adhesive layer 20, ultraviolet rays may be irradiated as necessary (refer to (g) of fig. 3). In the case where the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 20 is cured by ultraviolet rays, the pressure-sensitive adhesive layer 20 is cured, and the adhesive force between the pressure-sensitive adhesive layer 20 and the adhesive layer 30 can be reduced. In the ultraviolet irradiation, ultraviolet rays having a wavelength of 200 to 400nm can be used. The ultraviolet irradiation conditions were adjusted to the following conditions: 30-240 mW/cm²The lower irradiation dose is 200 to 500 mJ.

< picking-up Process >

Next, the semiconductor wafer 50 with the adhesive layer after dicing is separated from each other by expanding the base material film 10, while being lifted up from the base material film 10 side by the ejector pins 42, and the semiconductor wafer 50 with the adhesive layer is sucked by the suction chuck 44 to be picked up from the pressure-sensitive adhesive cured layer 20ac (refer to (h) of fig. 3). The semiconductor wafer 50 with an adhesive layer includes a semiconductor wafer Wa and an adhesive layer 30 a. The semiconductor chip Wa is obtained by dicing the semiconductor wafer W2, and the adhesive layer 30a is obtained by dicing the adhesive layer 30. The pressure-sensitive adhesive cured layer 20ac is obtained by cutting a pressure-sensitive adhesive cured layer obtained by curing a pressure-sensitive adhesive layer. The pressure-sensitive adhesive cured layer 20ac may remain on the substrate film 10 when the semiconductor wafer 50 with the adhesive layer is picked up. In the pickup step, the expansion is not always necessary, but the pickup property can be further improved by the expansion.

< semiconductor wafer bonding Process >

Next, after the semiconductor wafer 50 with the adhesive layer is picked up, the semiconductor wafer 50 with the adhesive layer is bonded to the support substrate 60 for mounting a semiconductor wafer by thermocompression bonding via the adhesive layer 30a (see (i) of fig. 3). A plurality of semiconductor wafers 50 with adhesive layers may be bonded to the support substrate 60 for mounting a semiconductor wafer. The adhesive layer 30a may be cured by heating at 120 to 150 ℃ for 0.5 to 6 hours, for example.

The semiconductor device shown in fig. 1 can be manufactured by a manufacturing method further including the steps of: the above-mentioned process; electrically connecting the semiconductor chip Wa to the semiconductor chip mounting support substrate 60 by bonding wires 70; and a step of resin-sealing the semiconductor wafer Wa on the surface 60a of the support substrate 60 for mounting a semiconductor wafer with the resin sealing material 80.

[ die bond film ]

The die bond film according to one embodiment is used for bonding a semiconductor wafer to a support member on which the semiconductor wafer is mounted. The grain bonding film has an elongation at break of 5% or less at-15 ℃. The die bonding film includes: the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer are contained in a total amount of 10 mass% or more and less than 30 mass%, based on the total amount of the epoxy resin, the epoxy resin curing agent, and the epoxy group-containing (meth) acrylic copolymer. The components, contents, and the like contained in the die bond film are the same as those exemplified in the adhesive layer. Therefore, a repetitive description will be omitted here.

[ dicing die-bonding integrated adhesive sheet ]

The dicing die-bonding integrated adhesive sheet of one embodiment includes, in order: an adhesive layer, a pressure-sensitive adhesive layer, and a base film, each of which is composed of the above-described die bond film.

Examples

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

< production of die bond film >

A varnish of the adhesive composition was prepared in the following order. The kinds and contents (solid contents) of the respective components are shown in table 1. First, an epoxy resin (A), an epoxy resin curing agent (B), an inorganic filler (D) and a silane coupling agent (E) are mixed, and cyclohexanone is added thereto and stirred. Subsequently, (C) an epoxy group-containing (meth) acrylic copolymer and (F) a curing accelerator were added, and vacuum degassing was performed to obtain a varnish of the adhesive composition.

The components in table 1 are as follows.

(A) The components: epoxy resin

(A1) Cresol novolak type epoxy resin (NIPPON STEEL Chemical & Material Co., Ltd., product name "YDCN-700-10", epoxy equivalent: 210g/eq)

(B) The components: epoxy resin curing agent

(B1) Phenol aralkyl type phenol resin (product name "Milex XLC-LL" manufactured by Mitsui Chemicals, Inc., softening point: 77 ℃ C., hydroxyl equivalent: 176g/eq)

(B2) Biphenyl aralkyl type phenol resin (product name: KAYAHARD GPH-103; softening point: 99-106 ℃ C., hydroxyl equivalent: 220-240 g/eq manufactured by Nippon Kayaku Co., Ltd.)

(C) The components: epoxy group-containing (meth) acrylic copolymer

(C1) Acrylic rubber (manufactured by Nagase Chemtex Corporation, trade name "HTR-860P-3", weight average molecular weight: 80 ten thousand, glass transition point: -13 ℃, butyl acrylate: ethyl acrylate: acrylonitrile: glycidyl methacrylate: 39.4:29.3:30.3:3.0 (mass ratio))

(D) The components: inorganic filler

(D1) Silica Filler (product name "SC 2050" manufactured by Admatechs Company Limited, average particle diameter: 0.5 μm, containing true spherical silica)

(D2) Silica Filler (product name "YA 050" manufactured by Admatechs Company Limited, average particle diameter: 0.05 μm, containing true spherical silica)

(E) The components: silane coupling agent

(E1) Gamma-mercaptopropyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC., trade name "A-189")

(E2)3- (N-phenyl) aminopropyltrimethoxysilane (phenylaminopropyltrimethoxysilane) (a silane coupling agent of the general formula (1), wherein R is methoxy and N is 3, and the silane coupling agent is manufactured by Momentive Performance Materials Japan LLC under the trade name of "Y9669")

(E3) Phenylaminomethyltrimethoxysilane (a silane coupling agent of the general formula (1) wherein R ═ is methoxy and n ═ 1, manufactured by Shin-Etsu Chemical co., ltd., trade name "X12-1191")

(F) The components: curing accelerator

(F1) 1-cyanoethyl-2-phenylimidazole (manufactured by SHIKOKU CHEMICALS CORPORATION, trade name "triazole (Curezol)2 PZ-CN")

Subsequently, the varnish of the obtained adhesive composition was coated on a polyethylene terephthalate (PET) film having a thickness of 38 μm as a support film and subjected to a release treatment. The coated varnish was dried by heating at 90 ℃ for 5 minutes and at 130 ℃ for 5 minutes. Thus, the die bond films of examples 1 to 3, comparative examples 1 and 2 having the thicknesses shown in table 1 were obtained in a semi-cured (B-stage) state on the support film.

Determination of elongation at Break at < -15 >

The die bond films of examples 1 to 3 and comparative examples 1 and 2 were cut into a width of 10mm and a length of 100mm, respectively, to prepare a sample for measuring elongation at break in a stripe shape. After the supporting film of the sample for measurement was peeled off and removed, it was set on Tencilon (Tensilon) (manufactured by Shimadzu Corporation, trade name "UTM-III-500") so that the distance between the jigs was 40 mm. Then, the film was cooled to-15 ℃ and the length of the film was measured while the film was stretched at a rate of 50 mm/min, and the length of the film at the time of film breakage was read. From the film length at the time of break and the initial film length (40mm), the elongation at break was calculated based on the following formula. The results are shown in Table 1.

Elongation at break (%) (length of film at break-initial length of film (40 mm))/initial length of film (40mm) × 100

< production of dicing die-bonding integrated adhesive sheet >

A dicing tape as a laminate of a pressure-sensitive adhesive layer and a base film was produced by applying an ultraviolet-curable pressure-sensitive adhesive (thickness: 10 μm) onto a base film (thickness: 100 μm, diameter: 370mm) comprising an ionomer resin. Next, the supporting film-attached die-bonding films (thickness: table 1, diameter: 312mm) of examples 1 to 3 and comparative examples 1 and 2 were prepared, and bonded so that the ultraviolet-curable pressure-sensitive adhesive of the dicing tape was in contact with the die-bonding films, to prepare dicing die-bonding integrated adhesive sheets of examples 1 to 3 and comparative examples 1 and 2, which were provided with an adhesive layer (die-bonding film), a pressure-sensitive adhesive layer (ultraviolet-curable pressure-sensitive adhesive), and a base film in this order.

< evaluation of fracture Property >

A semiconductor wafer having a thickness of 50 μm and a diameter of 300mm was prepared. The modified layer was formed on the semiconductor wafer so as to obtain a semiconductor chip of 4mm × 12mm using a stealth dicing laser saw (manufactured by DISCO CORPORATION, device name "DFL 7361"). Subsequently, back grinding was performed using a back grinding apparatus (manufactured by DISCO CORPORATION, under the apparatus name "DGP 8761") to adjust the thickness of the semiconductor wafer to 25 μm. The support films of the dicing die-bonding integrated adhesive sheets of examples 1 to 3 and comparative examples 1 and 2 were peeled off, and the adhesive layer (die bonding film) of the dicing die-bonding integrated adhesive sheet was laminated and attached to a semiconductor wafer having a thickness adjusted to 25 μm at 70 ℃. The semiconductor wafer with the dicing die-bonding integrated adhesive sheet was fixed, and the dicing tape was stretched at-15 ℃ using a stretching apparatus (manufactured by DISCO CORPORATION, under the apparatus name "DDS 2300"), to singulate the adhesive layer and the semiconductor wafer into semiconductor chips with adhesive layers of 4mm × 12 mm. At this time, the expansion conditions were adjusted so that the expansion rate was 100 mm/sec and the expansion amount was 8 mm. The singulated semiconductor chips were observed, and the case where both the adhesive layer and the semiconductor wafer were cut at the same time in a proportion of 90% or more of the total was regarded as good in cuttability and evaluated as "a", and the case where the adhesive layer and the semiconductor wafer were cut at less than 90% was regarded as poor in cuttability and evaluated as "B". The results are shown in Table 1.

< determination of shear Strength of Crystal grains >

The die-cut shear strength of the die-bond film was measured using the dicing die-bond integrated adhesive sheets of examples 1 to 3 having excellent cuttability. Semiconductor wafers for measuring the shear strength of crystal grains were produced as follows. A semiconductor wafer having a thickness of 400 μm was prepared, and the die bond film side of the dicing die-bond integrated adhesive sheets of examples 1 to 3 was laminated on the semiconductor wafer at a stage temperature of 70 ℃. The obtained cut sample was cut by using a full-automatic dicer DFD-6361 (manufactured by DISCO CORPORATION). In the cutting, cutting was performed by a stepwise cutting method using two blades, using cutting blades ZH05-SD2000-N1-70-FF and ZH05-SD4000-N1-70-EE (both manufactured by DISCO CORPORATION). The cutting conditions are blade rotation speed: 4000rpm, cutting speed: 50 mm/sec, wafer size: 5 mm. times.5 mm. In the cutting, the first stage cutting is performed so as to leave a semiconductor wafer of about 200 μm, and the second stage cutting is performed so as to form a cut of about 20 μm in the dicing tape. Subsequently, the pressure-sensitive adhesive layer composed of the ultraviolet-curable pressure-sensitive adhesive is irradiated with ultraviolet rays to cure the pressure-sensitive adhesive layer. Next, the semiconductor wafer to be picked up is picked up using the pickup chuck. In the picking, 5 pins in total, 1 pin in the center and 4 pins in the four corners, are used for jacking. The pick-up conditions were such that the jack-up speed was set to 20 mm/sec and the jack-up height was set to 450 μm. Thus, the semiconductor wafers with the die bond films of examples 1 to 3 were obtained. The semiconductor wafers with die bond films of examples 1 to 3 were bonded to a wiring board (organic substrate with solder resist, solder resist: TAIYO HOLDINGS co., ltd., trade name "AUS 308", unevenness on the substrate: about 6 μm) under conditions of a temperature of 120 ℃, a pressure of 0.1MPa, and a time of 1.0 second, and cured at 170 ℃ for 3 hours to prepare a sample of a cured product of the die bond film, which was measured at a measurement temperature of 250 ℃ using a universal adhesion tester (bond tester) (manufactured by Nordson Advanced Technology (Japan) k.k.k.k.. The results are shown in Table 1.

< evaluation of embeddability >

The embedding properties of the die bond film were evaluated using the dicing die bond integrated adhesive sheets of examples 1 to 3 having excellent cuttability. Semiconductor chips with die bond films of examples 1 to 3 for evaluation of embeddability were produced in the same manner as in production of semiconductor chips used for measurement of die shear strength except that semiconductor wafers having a thickness of 75 μm were prepared and the chip size was adjusted to 7.5mm × 7.5 mm. Samples were prepared by attaching the semiconductor wafers with die bond films of examples 1 to 3 to a wiring board (organic substrate with solder resist, TAIYO HOLDING GS CO., LTD., product name "AUS 308", unevenness on substrate: about 6 μm) at a temperature of 120 ℃ and a pressure of 0.15MPa for 1.0 second, and the samples were cured by heating at 150 ℃ for 6 hours on a hot plate. Then, the semiconductor wafer was sealed at 175 ℃ under 6.9MPa for 120 seconds using a molding sealant (product name "CEL-9700 HF" manufactured by Hitachi Chemical Company, ltd.) to produce a package for evaluation. The wiring board of the evaluation package was observed with an ultrasonic microscope to confirm the embeddability of irregularities on the board. The unevenness on the substrate was evaluated as "a" for good embeddability without voids, and "B" for poor embeddability with voids. The results are shown in Table 1.

[ Table 1]

The die bond films of examples 1 to 3 having an elongation at break at-15 ℃ of 5% or less are superior in the cuttability at the time of expansion to the die bond films of comparative examples 1 and 2 having an elongation at break at-15 ℃ of more than 5%. Further, it was confirmed that the die bond films of examples 1 to 3 are also excellent in the die shear strength and embeddability.

As described above, it was confirmed that the die bond film of the present invention is excellent in cuttability.

Description of the symbols

1-dicing die-bonding integrated adhesive sheet, 2-protective film, 4-modified layer, 10-base film, 20-pressure-sensitive adhesive layer, 20 ac-pressure-sensitive adhesive cured layer, 30 a-adhesive layer, 42-ejector pin, 44-suction chuck, 50-semiconductor chip with adhesive layer, 70-bonding wire, 60-supporting substrate for semiconductor chip mounting, 80-resin sealing material, 90-solder ball, W1, W2-semiconductor wafer, H1-thickness of semiconductor wafer W1, H2-thickness of semiconductor wafer W2, 100-semiconductor device.