WO2025263551A1 - Die bonding film and method for manufacturing same, dicing/die bonding integrated film and method for manufacturing same, and semiconductor device and method for manufacturing same - Google Patents

Abstract

Disclosed is a die bonding film. This die bonding film contains silver-containing particles produced through a reduction method, and a compound represented by formula (1). The silver-containing particle content is 70 mass% or more based on the total amount of the die bonding film. [In formula (1), R1, R2, R3, and R4 each independently represent a hydrogen atom, a halogen atom, a methyl group that may be substituted with a halogen atom, or an ethyl group that may be substituted with a halogen atom.　However, at least one of R1, R2, R3, and R4 is a halogen atom, a methyl group that may be substituted with a halogen atom, or an ethyl group that may be substituted with a halogen atom.]

Description

Die bonding film and manufacturing method thereof, dicing/die bonding integrated film and manufacturing method thereof, and semiconductor device and manufacturing method thereof

This disclosure relates to a die bonding film and its manufacturing method, a dicing/die bonding integrated film and its manufacturing method, and a semiconductor device and its manufacturing method.

Traditionally, semiconductor devices are manufactured through the following process. First, a semiconductor wafer is attached to a dicing adhesive sheet, and in this state, the semiconductor wafer is separated into semiconductor chips (dicing process). This is followed by an ultraviolet irradiation process, a pick-up process, a pressure-bonding process, a die-bonding process, etc. Patent Document 1 discloses an adhesive sheet (a dicing/die-bonding integrated film) that combines the function of fixing the semiconductor wafer in the dicing process and the function of bonding the semiconductor chip to the substrate in the die-bonding process. In the dicing process, the semiconductor wafer and adhesive layer are separated into individual chips with the adhesive layer attached.

In recent years, devices known as power semiconductor devices, which perform functions such as controlling electric power, have become widespread. Power semiconductor devices tend to generate heat due to the current supplied to them, and therefore require excellent heat dissipation properties. Patent Document 2 discloses a conductive die bonding film and a dicing tape with die bonding film (a dicing and die bonding integrated film) that exhibit higher heat dissipation properties after curing than before curing.

Japanese Patent Application Laid-Open No. 2008-218571 Patent No. 6396189

However, semiconductor devices manufactured using conventional die bonding films and integrated dicing and die bonding films do not have sufficient heat dissipation capabilities, and there is still room for improvement.

The present disclosure therefore aims to provide a die bonding film and an integrated dicing and die bonding film that enable the manufacture of semiconductor devices with excellent heat dissipation properties.

The inventors conducted extensive research to solve the above problems and discovered that the thermal conductivity of a die bonding film can be improved by incorporating silver-containing particles that have been surface-treated with a surface treatment agent and a specific compound into the die bonding film, leading to the completion of the disclosed invention.

The present disclosure provides a method for producing a die bonding film according to [1] to [7], a method for producing a dicing/die bonding integrated film according to [8], a method for producing a semiconductor device according to [9], a die bonding film according to [10] to [12], a dicing/die bonding integrated film according to [13], and a semiconductor device according to [14].
[1] A first step of preparing a raw material varnish containing silver-containing particles produced by a reduction method, a compound represented by formula (1), and an organic solvent;
a second step of mixing the raw varnishes to obtain an adhesive varnish;
a third step of applying the adhesive varnish to a support film and removing the organic solvent to obtain a die-bonding film;
Equipped with
the content of the silver-containing particles is 70 mass% or more based on the total solid content of the adhesive varnish;
A method for manufacturing a die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.]
[2] a first step of preparing a raw material varnish containing silver-containing particles surface-treated with a surface treatment agent, a compound represented by formula (1), and an organic solvent;
a second step of mixing the raw varnishes to obtain an adhesive varnish;
a third step of applying the adhesive varnish to a support film and removing the organic solvent to obtain a die-bonding film;
Equipped with
the content of the silver-containing particles is 70 mass% or more based on the total solid content of the adhesive varnish;
A method for manufacturing a die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.]
[3] The second step is a step of mixing the raw varnish under a temperature condition of 50°C or higher.
[1] or [2], the method for producing the die bonding film.
[4] The raw varnish further contains a thermosetting resin, a curing agent, and an elastomer.
[1] - [3] The method for producing a die bonding film according to any one of [1] to [3].
[5] The thermosetting resin contains an epoxy resin that is liquid at 25°C.
[4] A method for producing a die bonding film according to [4].
[6] The second step is a step of adding a thermosetting resin, a curing agent, and an elastomer to the mixed raw varnish to obtain an adhesive varnish further containing these.
[1] - [3] The method for producing a die bonding film according to any one of [1] to [3].
[7] The thermosetting resin contains an epoxy resin that is liquid at 25°C.
[6] A method for producing a die bonding film according to [6].
[8] preparing a dicing tape having a base layer and a pressure-sensitive adhesive layer provided on the base layer;
A step of bonding a die bonding film manufactured by the die bonding film manufacturing method according to any one of [1] to [7] and the pressure-sensitive adhesive layer of the dicing tape together to form an adhesive layer made of the die bonding film on the pressure-sensitive adhesive layer;
Equipped with
A manufacturing method for integrated dicing and die bonding film.
[9] A step of attaching the adhesive layer of the dicing and die bonding integrated film manufactured by the manufacturing method of the dicing and die bonding integrated film according to [8] to a semiconductor wafer;
singulating the semiconductor wafer and the adhesive layer;
picking up the semiconductor chip with the adhesive layer piece from the dicing tape;
a step of adhering the semiconductor chip with the adhesive layer piece to a support member via the adhesive layer piece;
Equipped with
A method for manufacturing a semiconductor device.
[10] A silver-containing particle produced by a reduction method and a compound represented by formula (1),
The content of the silver-containing particles is 70 mass% or more based on the total amount of the die bonding film.
Die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.]
[11] Further containing a thermosetting resin, a curing agent, and an elastomer,
The die bonding film according to [10].
[12]
The thermosetting resin includes an epoxy resin that is liquid at 25°C.
The die bonding film according to [11].
[13] A dicing tape having a base layer and a pressure-sensitive adhesive layer provided on the base layer;
An adhesive layer made of the die bonding film according to any one of [10] to [12], which is disposed on the pressure-sensitive adhesive layer of the dicing tape;
Equipped with
Integrated dicing and die bonding film.
[14] A semiconductor chip;
a support member on which the semiconductor chip is mounted;
an adhesive member provided between the semiconductor chip and the support member, the adhesive member bonding the semiconductor chip and the support member;
Equipped with
The adhesive member comprises a cured product of the die bonding film according to any one of [10] to [12].
Semiconductor device.

The present disclosure provides a die bonding film and a dicing/die bonding integrated film that can be used to manufacture semiconductor devices with excellent heat dissipation properties. The present disclosure also provides methods for manufacturing these. Furthermore, the present disclosure provides a semiconductor device using such a die bonding film, and a method for manufacturing a semiconductor device using a dicing/die bonding integrated film.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a die bonding film. FIG. 2 is a schematic cross-sectional view showing one embodiment of a dicing and die bonding integrated film. 3A, 3B, 3C, 3D, 3E, and 3F are schematic cross-sectional views illustrating each step of a method for manufacturing a semiconductor device according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device.

Embodiments of the present disclosure will be described below, with appropriate reference to the drawings. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including steps, etc.) are not essential unless specifically stated. The sizes of the components in each figure are conceptual, and the relative size relationships between the components are not limited to those shown in each figure.

The same applies to the numerical values and ranges in this specification, and do not limit the present disclosure. In this specification, numerical ranges indicated using "to" indicate ranges that include the numerical values before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with the value shown in the examples.

In this specification, "(meth)acrylate" means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl." Furthermore, "(poly)" refers to both the presence and absence of the "poly" prefix. Furthermore, "A or B" may include either A or B, or may include both. Furthermore, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of those multiple substances present in the composition, unless otherwise specified.

[Die bonding film]
Fig. 1 is a schematic cross-sectional view showing one embodiment of a die bonding film. The die bonding film 10A shown in Fig. 1 may be provided on a support film 20, as shown in Fig. 1. The die bonding film 10A is thermosetting and can go through a semi-cured (B-stage) state and then into a cured (C-stage) state after a curing treatment.

The die bonding film 10A contains silver-containing particles (component (a)) produced by a reduction method or silver-containing particles surface-treated (coated) with a surface treatment agent, and a compound (component (b)) represented by formula (1). If necessary, the die bonding film 10A may further contain a thermosetting resin (component (c)), a curing agent (component (d)), and an elastomer (component (e)).

Component (a): Silver-containing particles produced by a reduction method or silver-containing particles surface-treated (coated) with a surface treatment agent. Component (a) is a component used to increase the thermal conductivity of die bonding films and improve the heat dissipation properties of semiconductor devices. The silver-containing particles may be, for example, particles composed of silver (particles composed of silver alone, silver particles) or silver-coated metal particles in which the surfaces of metal particles (copper particles, etc.) are coated with silver. Examples of silver-coated metal particles include silver-coated copper particles. Component (a) may be particles composed of silver (silver particles).

Component (a) may be silver particles produced by a reduction method (silver particles produced by a liquid-phase (wet) reduction method using a reducing agent). In a liquid-phase (wet) reduction method using a reducing agent, a surface treatment agent (lubricant) is typically added to control particle size and prevent aggregation and fusion, and the surface of silver particles produced by a liquid-phase (wet) reduction method using a reducing agent is treated (coated) with the surface treatment agent (lubricant). In other words, silver particles (silver-containing particles) produced by a reduction method are typically surface-treated with a surface treatment agent (lubricant). Examples of surface treatment agents include fatty acid compounds such as oleic acid (melting point: 13.4°C), myristic acid (melting point: 54.4°C), palmitic acid (melting point: 62.9°C), and stearic acid (melting point: 69.9°C); fatty acid amide compounds such as oleic acid amide (melting point: 76°C) and stearic acid amide (melting point: 100°C); fatty alcohol compounds such as pentanol (melting point: -78°C), hexanol (melting point: -51.6°C), oleyl alcohol (melting point: 16°C), and stearyl alcohol (melting point: 59.4°C); and fatty nitrile compounds such as oleanitrile (melting point: -1°C). The surface treatment agent may have a low melting point (e.g., a melting point of 100°C or less) and high solubility in organic solvents, such as a fatty acid compound. That is, component (a) may be silver particles (silver-containing particles) surface-treated (coated) with a fatty acid compound.

The shape of component (a) is not particularly limited and may be, for example, flake-like, plate-like, needle-like, spherical, etc., or may even be spherical. When component (a) is spherical, it tends to be easier to obtain a die bonding film with improved surface roughness (Ra).

The average particle size of component (a) may be 0.01 to 10 μm. An average particle size of component (a) of 0.01 μm or more prevents an increase in viscosity when the adhesive varnish is prepared, allows the desired amount of component (a) to be contained in the die bonding film, and tends to ensure the wettability of the die bonding film to the adherend, thereby exhibiting better adhesion. An average particle size of component (a) of 10 μm or less tends to provide better film formability and improve thermal conductivity through the addition of component (a), thereby improving the heat dissipation properties of the semiconductor device. Furthermore, by setting the particle size within this range, the thickness of the die bonding film can be made thinner, allowing for a higher stacking density of semiconductor chips and tending to prevent chip cracks caused by conductive particles protruding from the die bonding film. The average particle size of component (a) may be 0.1 μm or more, 0.5 μm or more, or 1.0 μm or more, or 8.0 μm or less, 5.0 μm or less, or 3.0 μm or less.

In this specification, the average particle size of component (a) refers to the particle size (laser 50% particle size ( _D50 )) when the ratio (volume fraction) of component (a) to the total volume of component (a) is 50%. The average particle size ( _D50 ) can be determined by measuring a suspension of component (a) in water by a laser scattering method using a laser scattering particle size measuring device (e.g., Microtrac).

The content of component (a) is 70% by mass or more, based on the total amount of the die bonding film (or the total solids content of the adhesive varnish described below). When the content of component (a) is 70% by mass or more, based on the total amount of the die bonding film, the thermal conductivity of the die bonding film can be improved, and as a result, heat dissipation properties can be improved. The content of component (a) may be 72% by mass or more, 74% by mass or more, or 75% by mass or more, based on the total amount of the die bonding film. There is no particular upper limit for the content of component (a), but it may be 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on the total amount of the die bonding film. When the content of component (a) is 90% by mass or less, based on the total amount of the die bonding film, other components can be more sufficiently contained in the die bonding film. This ensures the wettability of the die bonding film to the adherend and allows for better adhesion.

The content of component (a) may be 24.0 volume % or more, 24.5 volume % or more, or 25.0 volume % or more, based on the total amount (total volume) of the die bonding film. When the content of component (a) is 24.0 volume % or more, based on the total amount (total volume) of the die bonding film, the thermal conductivity of the die bonding film can be improved, and as a result, the heat dissipation performance of the semiconductor device can be improved. The content of component (a) may be 33.0 volume % or less, 30.0 volume % or less, or 28.0 volume % or less, based on the total amount (total volume) of the die bonding film. When the content of component (a) is 33.0 volume % or less, based on the total amount (total volume) of the die bonding film, other components can be more sufficiently contained in the die bonding film. This ensures the wettability of the die bonding film to the adherend and allows for better adhesion.

The content (volume %) of the component (a) can be calculated from the following formula (I), for example, when the density of the die bonding film is x (g/cm ³ ), the density of the component (a) is y (g/cm ³ ), and the mass proportion of the component (a) in the die bonding film is z (mass %). The mass proportion of the component (a) in the die bonding film can be determined by performing thermogravimetric analysis using, for example, a thermogravimetric differential thermal analyzer (TG-DTA). The densities of the die bonding film and the component (a) can be determined by measuring the mass and specific gravity using a hydrometer.
(a) Component content (volume %) = (x/y) × z (I)
TG-DTA measurement conditions: temperature range 30 to 600°C (heating rate 30°C/min), maintained at 600°C for 20 minutes; air flow rate: 300 mL/min; thermogravimetric differential thermal analyzer: TG/DTA220, manufactured by Seiko Instruments Inc.
Hydrometer: Alpha Mirage Co., Ltd., EW-300SG

Component (b): A compound represented by formula (1) The die bonding film 10A contains component (b). When the die bonding film contains components (a) and (b), the thermal conductivity of the die bonding film can be improved, and as a result, the heat dissipation performance of the semiconductor device can be improved.

In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.

Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

A methyl group that may be substituted with a halogen atom refers to an unsubstituted methyl group or a methyl group in which at least one hydrogen atom has been substituted with a halogen atom. Examples of methyl groups substituted with a halogen atom include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, and a trifluoromethyl group.

An ethyl group that may be substituted with a halogen atom refers to an unsubstituted ethyl group or an ethyl group in which at least one hydrogen atom has been substituted with a halogen atom. Examples of ethyl groups substituted with a halogen atom include a fluoroethyl group, a chloroethyl group, a bromoethyl group, an iodoethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a perfluoroethyl group.

At least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom. Among these, at least one of R ¹ , R ² , R ³ , and R ⁴ may be a methyl group. Among R ¹ , R ² , R ³ , and R ⁴ , the number of halogen atoms, methyl groups optionally substituted with a halogen atom, and ethyl groups optionally substituted with a halogen atom may be one. That is, one of R ¹ , R ² , R ³ , and R ⁴ may be a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom, and the remaining three of R ¹ , R ² , R ³ , and R ⁴ may be hydrogen atoms.

Examples of compounds represented by formula (1) that satisfy these conditions include 2-methylglutaric acid, 2-ethylglutaric acid, 2-fluoroglutaric acid, 2-chloroglutaric acid, 2-bromoglutaric acid, 2-iodoglutaric acid, 2-(trifluoromethyl)glutaric acid, 2-(difluoromethyl)glutaric acid, 2-(chloromethyl)glutaric acid, 2-(fluoromethyl)glutaric acid, 2-(dichloromethyl)glutaric acid, 2-(trichloromethyl)glutaric acid, 2-(2-fluoroethyl)glutaric acid, 2-(2,2,2-trifluoroethyl)glutaric acid, 2-(2-chloroethyl)glutaric acid, and 2-(2,2-difluoroethyl)glutaric acid. Among these, the compound represented by formula (1) may contain 2-methylglutaric acid.

The content of component (b) may be 0.1 to 5 parts by mass when the total amount of component (a) is taken as 100 parts by mass. When the content of component (b) is 0.1 part by mass or more when the total amount of component (a) is taken as 100 parts by mass, the thermal conductivity of the die bonding film tends to be further improved. When the content of component (b) is 5 parts by mass or less when the total amount of component (a) is taken as 100 parts by mass, the amounts of other components (particularly components (c), (d), and (e)) can be sufficiently secured, and the film formability tends to be excellent.

The content of component (b) may be 0.2% by mass or more, or 0.3% by mass or more, and may be 3% by mass or less, or 2% by mass or less, based on the total amount of the die bonding film (or the total amount of solids in the adhesive varnish described below).

Component (c): Thermosetting Resin Component (c) is a component that has the property of forming three-dimensional bonds between molecules and curing when heated, etc., and is a component that exhibits adhesive properties after curing. Component (c) may be an epoxy resin. Component (c) may contain an epoxy resin that is liquid at 25°C. Any epoxy resin can be used without particular limitations as long as it has an epoxy group in the molecule. Epoxy resins may have two or more epoxy groups in the molecule.

Examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, stilbene epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane epoxy resins, biphenyl epoxy resins, xylylene epoxy resins, biphenyl aralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene. Among these, the epoxy resin may be a bisphenol epoxy resin or a cresol novolac epoxy resin from the viewpoint of heat resistance of the cured product.

The epoxy resin may contain an epoxy resin that is liquid at 25°C (hereinafter, sometimes simply referred to as "liquid epoxy resin"). By including such a liquid epoxy resin, it tends to be easier to obtain a die bonding film with improved surface roughness (Ra). Examples of commercially available liquid epoxy resins include EXA-830CRP (trade name, manufactured by DIC Corporation) and YDF-8170C (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.).

The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90 to 300 g/eq or 110 to 290 g/eq. When the epoxy equivalent of the epoxy resin is within this range, it tends to be easier to ensure the fluidity of the adhesive composition when forming the die bonding film while maintaining the bulk strength of the die bonding film.

The content of component (c) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 15% by mass or less, 12% by mass or less, or 10% by mass or less, based on the total amount of the die bonding film (or the total amount of solids in the adhesive varnish described below).

When component (c) contains a liquid epoxy resin, the mass ratio of the amount of liquid epoxy resin to the total amount of component (c) (amount (mass) of liquid epoxy resin / total amount (total mass) of components (c)) may be, in percentage, 20% or more, 30% or more, 40% or more, or 50% or more, and may be 100% or less, 90% or less, 80% or less, or 70% or less.

Component (d): Curing Agent Component (d) may be a phenolic resin that can serve as a curing agent for epoxy resins. Any phenolic resin can be used without particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of phenolic resins include novolak-type phenolic resins obtained by condensing or co-condensing 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 a compound having an aldehyde group such as formaldehyde, under an acidic catalyst; allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolak, and phenol aralkyl resins, naphthol aralkyl resins, biphenyl aralkyl-type phenolic resins, and phenyl aralkyl-type phenolic resins synthesized from phenols such as phenol and/or naphthols with dimethoxy-para-xylene or bis(methoxymethyl)biphenyl.

The hydroxyl equivalent of the phenolic resin may be 40 to 300 g/eq, 70 to 290 g/eq, or 100 to 280 g/eq. If the hydroxyl equivalent of the phenolic resin is 40 g/eq or more, the storage modulus of the film tends to be further improved, and if it is 300 g/eq or less, defects due to the generation of foaming, outgassing, etc. can be prevented.

From the standpoint of curing properties, the ratio of the epoxy equivalent of the epoxy resin (component (c)) to the hydroxyl equivalent of the phenolic resin (component (d)) (epoxy equivalent of the epoxy resin (component (c)) / hydroxyl equivalent of the phenolic resin (component (d)) may be 0.30/0.70 to 0.70/0.30, 0.35/0.65 to 0.65/0.35, 0.40/0.60 to 0.60/0.40, or 0.45/0.55 to 0.55/0.45. When this equivalent ratio is 0.30/0.70 or higher, more sufficient curing properties tend to be obtained. When this equivalent ratio is 0.70/0.30 or lower, excessive viscosity increase can be prevented, and more sufficient fluidity can be obtained.

The content of component (d) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 15% by mass or less, 12% by mass or less, or 10% by mass or less, based on the total amount of the die bonding film (or the total amount of solids in the adhesive varnish described below).

Component (e): Elastomer Examples of component (e) include acrylic resins (including acrylic rubber), urethane resins (including urethane rubber), silicone resins (including silicone rubber), and styrene-based elastomers. Component (e) may be any of these resins having a crosslinkable functional group, or may be an acrylic resin having a crosslinkable functional group. Here, the acrylic resin refers to a polymer containing a structural unit derived from a (meth)acrylic acid ester. The acrylic resin may be a polymer containing a structural unit derived from a (meth)acrylic acid ester having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxy group. The acrylic resin may also be an acrylic rubber, such as a copolymer of a (meth)acrylic acid ester and acrylonitrile.

Commercially available acrylic resins include, for example, SG-P3, SG-70L, SG-708-6, WS-023 EK30, and SG-280 EK23 (all manufactured by Nagase ChemteX Corporation).

The glass transition temperature (Tg) of component (e) may be -50 to 50°C or -30 to 20°C. If the Tg of the acrylic resin is -50°C or higher, the tackiness of the die bonding film will be reduced, tending to improve handleability. If the Tg of the acrylic resin is 50°C or lower, the fluidity of the adhesive composition when forming the die bonding film will tend to be more sufficiently ensured. Here, the Tg of component (e) refers to the value measured using a DSC (differential scanning calorimeter) (for example, Thermo Plus 2, manufactured by Rigaku Corporation).

The weight average molecular weight (Mw) of component (e) may be 50,000 to 1.6 million, 100,000 to 1.4 million, or 300,000 to 1.2 million. When component (e) has an Mw of 50,000 or more, the film-forming properties tend to be better. When component (e) has an Mw of 1.6 million or less, the adhesive composition tends to have better fluidity when forming a die-bonding film. Note that Mw is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

The Mw of component (e) was measured using the following equipment and under the following conditions.
Pump: L-6000 (manufactured by Hitachi, Ltd.)
Column: A column consisting of Gelpack GL-R440 (manufactured by Resonac Co., Ltd.), Gelpack GL-R450 (manufactured by Resonac Co., Ltd.), and Gelpack GL-R400M (manufactured by Resonac Co., Ltd.) (each 10.7 mm (diameter) × 300 mm) connected in this order. Eluent: Tetrahydrofuran (hereinafter referred to as "THF")
Sample: 120 mg of sample dissolved in 5 mL of THF Flow rate: 1.75 mL/min

The content of component (e) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 15% by mass or less, 12% by mass or less, or 10% by mass or less, based on the total amount of the die bonding film (or the total amount of solids in the adhesive varnish described below).

Component (f): Curing Accelerator The die bonding film 10A may further contain a curing accelerator (component (f)). When the die bonding film contains component (f), it tends to be able to achieve a better balance between adhesiveness and connection reliability. Examples of component (f) include imidazoles and their derivatives, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, component (f) may be imidazoles and their derivatives from the viewpoint of reactivity.

Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

The content of component (f) may be 0.001 to 1 mass% based on the total amount of the die bonding film (or the total solids content of the adhesive varnish described below). When the content of component (f) is within this range, it tends to be possible to achieve a better balance between adhesiveness and connection reliability.

The die bonding film 10A may further contain other components in addition to components (a) to (f), such as coupling agents, antioxidants, rheology control agents, and leveling agents. Examples of coupling agents include 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane. The content of these other components may be 0.01 to 3% by mass, based on the total mass of the die bonding film.

[Method for manufacturing die bonding film]
The die bonding film 10A shown in FIG. 1 can be obtained by a method comprising a first step of preparing a raw material varnish containing component (a) (silver-containing particles produced by a reduction method or silver-containing particles surface-treated with a surface treatment agent), component (b), and an organic solvent; a second step of mixing the raw material varnish to obtain an adhesive varnish; and a third step of applying the adhesive varnish to a support film and removing the organic solvent to obtain a die bonding film.

The first step is to prepare a raw varnish containing component (a) (silver-containing particles produced by a reduction method or silver-containing particles surface-treated with a surface treatment agent), component (b), and an organic solvent.

The organic solvent is not particularly limited as long as it can dissolve components other than component (a). Examples of organic solvents 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, and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Among these, the organic solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone from the standpoint of solubility and boiling point. The solids concentration in the raw varnish may be 10 to 80% by mass based on the total amount of the raw varnish.

The raw varnish can be obtained, for example, by adding each component to a container used in a mixer. In this case, the order in which each component is added is not particularly limited and can be set appropriately depending on the properties of each component.

The second step is to mix the raw varnishes to obtain the adhesive varnish.

Mixing can be carried out using an appropriate combination of conventional mixers such as a Homo Disper, Three-One Motor, mixing rotor, planetary, or mortar mixer. The mixer may be equipped with heating equipment such as a heater unit that can control the temperature conditions of the raw varnish (or adhesive varnish). When a Homo Disper is used for mixing, the rotation speed of the Homo Disper may be 4,000 rpm or more.

The second step may be a step of mixing the raw varnish at a temperature of 50°C or higher. The mixing temperature may be adjusted as necessary using heating equipment, heat-retaining equipment, etc. If the mixing temperature is 50°C or higher, for example, the resulting die bonding film is more likely to form a sintered body of component (a) in the cured product (C-stage) state after the curing treatment, thereby further improving the thermal conductivity of the die bonding film. The mixing temperature may be 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher. The upper limit of the mixing temperature may be, for example, 120°C or lower, 110°C or lower, 100°C or lower, 90°C or lower, or 80°C or lower. The mixing time may be, for example, 1 minute or more, 5 minutes or more, 10 minutes or more, or 20 minutes or more, or 80 minutes or less, 60 minutes or less, or 40 minutes or less.

Components (c), (d), (e), (f), and other components can be independently incorporated into the raw varnish or adhesive varnish at any stage, depending on the properties of each component. For example, a raw varnish further containing these components may be prepared in the first step, and the raw varnishes may be mixed in the second step to obtain an adhesive varnish containing components (a), (b), (c), (d), (e), (f), and other components. Alternatively, for example, raw varnishes may be prepared in the first step, and the raw varnishes may be mixed in the second step, and these components may be added to the mixed raw varnish to obtain an adhesive varnish containing components (a), (b), (c), (d), (e), (f), and other components. Furthermore, for example, a raw varnish further containing components (c) and (d) may be prepared in the first step, and the raw varnishes may be mixed in the second step, followed by adding components (e), (f), and other components to the mixed raw varnish to obtain an adhesive varnish containing components (a), (b), (c), (d), (e), (f), and other components. When at least one component selected from the group consisting of components (c), (d), (e), (f), and other components is added to the mixed raw varnish in the second step, mixing may be performed at a temperature below 50°C (e.g., room temperature (25°C)) after the addition of the component. In this case, the mixing may be performed at room temperature (25°C) for 0.1 to 48 hours.

In this way, an adhesive varnish containing the specified components can be obtained. The resulting adhesive varnish may be subjected to vacuum degassing or other methods to remove air bubbles from the varnish.

The content of component (a) is 70% by mass or more, based on the total solid content of the adhesive varnish. In this specification, the solid content of the adhesive varnish means the total amount of components other than the organic solvent. The content of component (a) may be 72% by mass or more, 74% by mass or more, or 75% by mass or more, based on the total solid content of the adhesive varnish, or may be 90% by mass or less, 85% by mass or less, or 80% by mass or less.

The third step is to apply adhesive varnish to the support film 20 and remove the organic solvent to obtain the die bonding film 10A.

The support film 20 is not particularly limited, and examples include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, etc. The support film may be subjected to a release treatment. The thickness of the support film 20 may be, for example, 10 to 200 μm or 20 to 170 μm.

The adhesive varnish can be applied to the support film 20 using known methods, such as knife coating, roll coating, spray coating, gravure coating, bar coating, and curtain coating.

After applying the adhesive varnish to the support film, the organic solvent can be removed by heat drying. There are no particular restrictions on the heat drying conditions as long as they sufficiently volatilize the organic solvent used. For example, the heat drying temperature may be 50 to 200°C, and the heat drying time may be 0.1 to 30 minutes. Heat drying may also be carried out in stages using different heat drying temperatures or heat drying times.

The thickness of the die bonding film 10A can be adjusted appropriately depending on the application, but may be, for example, 3 to 200 μm. If the thickness of the die bonding film 10A is 3 μm or more, the adhesive strength with the semiconductor wafer tends to be sufficient, and if it is 200 μm or less, the thermal conductivity tends to be sufficient. The thickness of the die bonding film 10A may be 5 to 100 μm or 10 to 50 μm, from the perspective of adhesive strength and thinning the semiconductor device.

The thermal conductivity (25°C ± 1°C) of the die bonding film 10A after thermal curing at 170°C for 3 hours (C-stage state) may be 4.0 W/(m·K) or more. A thermal conductivity of 4.0 W/(m·K) or more tends to improve the heat dissipation properties of the semiconductor device. The thermal conductivity may be 4.5 W/(m·K) or more, 5.0 W/(m·K) or more, 5.5 W/(m·K) or more, or 6.0 W/(m·K) or more. There is no particular upper limit to the thermal conductivity (25°C ± 1°C) of the die bonding film 10A in the C-stage state, but it may be 30 W/(m·K) or less.

The thermal conductivity (25°C ± 1°C) of die bonding film 10A after thermal curing at 170°C for 3 hours (C-stage state) can be measured, for example, by the following method. First, the die bonding film is cut to a predetermined size, and a predetermined number of film pieces are prepared so that the thickness when laminated will be 200 μm. For example, if a die bonding film with a thickness of 25 μm is used, eight film pieces are prepared. If a die bonding film with a thickness of 10 μm is used, 20 film pieces are prepared. These film pieces are laminated using a rubber roll on a hot plate at 70°C to prepare a laminate with a thickness of 200 μm. Next, each laminate is thermally cured at 170°C for 3 hours in a clean oven (manufactured by Espec Corporation) to obtain a sample in a C-stage state. The obtained sample is cut into 1 cm x 1 cm pieces, and this is used as a thermal conductivity measurement film. Thermal conductivity is measured under the following measurement items/conditions.

(Calculation of thermal conductivity)
The thermal conductivity λ of the film for measuring thermal conductivity in the thickness direction is calculated by the following formula.
Thermal conductivity λ (W/(m・K)) = Thermal diffusivity α (m ² /s) × Specific heat Cp (J/(kg・K)) × Density ρ (g/cm ³ )

The thermal diffusivity α, specific heat Cp, and density ρ are measured using the following methods. A high thermal conductivity λ means that the semiconductor device has better heat dissipation properties.

(Measurement of thermal diffusivity α)
A measurement sample is prepared by blackening both sides of a thermal conductivity measurement film with graphite spray. The thermal diffusivity α of the measurement sample is determined by the laser flash method (xenon flash method) using, for example, the following measurement device under the following conditions.
Measurement device: Thermal diffusivity measurement device (manufactured by Netsch Japan Co., Ltd., product name: LFA447 nanoflash)
Pulse width of pulsed light irradiation: 0.1 ms
・Applied voltage for pulsed light irradiation: 236V
・Measurement sample treatment: Both sides of the thermal conductivity measurement film are blackened with graphite spray. ・Measurement ambient temperature: 25°C ± 1°C

(Measurement of specific heat Cp (25°C))
The specific heat Cp (25° C.) of the film for measuring thermal conductivity is determined, for example, by carrying out differential scanning calorimetry (DSC) using the following measuring device under the following conditions.
Measurement device: differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., product name: Pyris1)
Reference material: sapphire Heating rate: 10°C/min Heating temperature range: room temperature (25°C) to 60°C

(Measurement of density ρ)
The density ρ of the film for measuring thermal conductivity is measured, for example, by the Archimedes method using the following measuring device under the following conditions.
Measuring device: Electronic hydrometer (manufactured by Alpha Mirage Co., Ltd., product name: SD200L)
・Water temperature: 25℃

By containing components (a) and (b), the die bonding film can improve thermal conductivity, thereby improving the heat dissipation properties of semiconductor devices. Therefore, the die bonding film can be combined with a dicing tape (dicing film) having an adhesive layer and used as an integrated dicing and die bonding film.

[Dicing and die bonding integrated film]
Fig. 2 is a schematic cross-sectional view showing one embodiment of a dicing/die bonding integrated film. The dicing/die bonding integrated film 100 shown in Fig. 2 includes a dicing tape 50 (dicing film) including a base layer 40 and a pressure-sensitive adhesive layer 30 provided on the base layer 40, and an adhesive layer 10 consisting of a die bonding film 10A provided on the pressure-sensitive adhesive layer 30 of the dicing tape 50. The dicing/die bonding integrated film 100 may be in the form of a film, sheet, tape, or the like. The dicing/die bonding integrated film 100 may also include a support film 20 on the surface of the adhesive layer 10 opposite the pressure-sensitive adhesive layer 30.

The substrate layer 40 in the dicing tape 50 may be, for example, a plastic film such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, or polyimide film. Furthermore, the substrate layer 40 may be subjected to surface treatments such as primer application, UV treatment, corona discharge treatment, polishing, or etching, as needed.

The adhesive layer 30 in the dicing tape 50 is not particularly limited as long as it has sufficient adhesive strength to prevent the semiconductor chips from scattering during dicing, and low enough adhesive strength not to damage the semiconductor chips in the subsequent semiconductor chip pick-up process, and any adhesive known in the field of dicing tape can be used. The adhesive layer 30 may be an adhesive layer made of a non-UV-curable adhesive, or an adhesive layer made of a UV-curable adhesive. If the adhesive layer is an adhesive layer made of a UV-curable adhesive, the adhesiveness of the adhesive layer can be reduced by irradiating it with UV light.

The thickness of the dicing tape 50 (base layer 40 and adhesive layer 30) may be 60 to 150 μm or 70 to 130 μm from the standpoints of economy and film handling.

The dicing and die bonding integrated film 100 shown in Figure 2 can be obtained by a manufacturing method that includes the steps of preparing a die bonding film 10A and a dicing tape 50 that includes a base layer 40 and an adhesive layer 30 provided on the base layer 40, and bonding the die bonding film 10A to the adhesive layer 30 of the dicing tape 50. A known method can be used to bond the die bonding film 10A to the adhesive layer 30 of the dicing tape 50.

[Semiconductor device and manufacturing method thereof]
3A, 3B, 3C, 3D, 3E, and 3F are schematic cross-sectional views illustrating each step of a method for manufacturing a semiconductor device according to an embodiment of the present invention. The method for manufacturing a semiconductor device includes a step of attaching a semiconductor wafer W to the adhesive layer 10 of the above-mentioned dicing/die bonding integrated film 100 (wafer lamination step, see Figures 3(a) and (b)), a step of singulating the semiconductor wafer W and the adhesive layer 10 (dicing step, see Figure 3(c)), a step of irradiating the adhesive layer 30 (through the base layer 40) with ultraviolet light (ultraviolet irradiation step, see Figure 3(d)), a step of picking up the semiconductor chip 60 with adhesive layer piece from the dicing tape 50 (the adhesive layer 30 of the dicing tape 50) (pickup step, see Figure 3(e)), a step of adhering the semiconductor chip 60 with adhesive layer piece to a support member 80 through the adhesive layer piece 10a (semiconductor chip adhering step, see Figure 3(f)), and a step of thermally curing the adhesive layer piece 10a in the semiconductor chip 60 with adhesive layer piece adhered to the support member 80, if necessary (thermal curing step).

<Wafer lamination process>
In this process, first, the dicing and die bonding integrated film 100 is placed in a predetermined device. Then, the front surface Ws of the semiconductor wafer W is attached to the adhesive layer 10 of the dicing and die bonding integrated film 100 (see FIGS. 3(a) and 3(b)). The circuit surface of the semiconductor wafer W may be provided on the surface opposite to the front surface Ws.

Semiconductor wafers W include, for example, single crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.

<Dicing process>
In this step, the semiconductor wafer W and the adhesive layer 10 are diced into individual pieces (see FIG. 3(c)). At this time, a part of the pressure-sensitive adhesive layer 30, or the entire pressure-sensitive adhesive layer 30 and a part of the base material layer 40 may be diced into individual pieces. In this way, the dicing and die-bonding integrated film 100 also functions as a dicing sheet.

<Ultraviolet irradiation process>
When the adhesive layer 30 is an adhesive layer made of an ultraviolet-curable adhesive, the method for manufacturing a semiconductor device may include an ultraviolet irradiation step. In this step, ultraviolet light is irradiated onto the adhesive layer 30 (through the base layer 40) (see FIG. 3(d)). The wavelength of the ultraviolet light may be 200 to 400 nm. The ultraviolet light irradiation conditions may be such that the illuminance and dose are in the ranges of 30 to 240 mW/ ^cm² and 50 to 500 mJ/ ^cm² , respectively.

<Pickup process>
In this process, the base layer 40 is expanded to separate the individual semiconductor chips 60 with adhesive layer pieces from each other, and the semiconductor chips 60 with adhesive layer pieces pushed up from the base layer 40 side by the needles 72 are sucked with a suction collet 74 and picked up from the adhesive layer 30a (see FIG. 3(e)). The semiconductor chips 60 with adhesive layer pieces include a semiconductor chip Wa and an adhesive layer piece 10a. The semiconductor chip Wa is obtained by dividing the semiconductor wafer W, and the adhesive layer piece 10a is obtained by dividing the adhesive layer 10. The adhesive layer 30a is obtained by dividing the adhesive layer 30. The adhesive layer 30a may remain on the base layer 40 after the semiconductor chips 60 with adhesive layer pieces are picked up. In this process, expanding the base layer 40 is not necessarily required, but expanding the base layer 40 can further improve pickup properties.

The amount of thrust by the needle 72 can be set as appropriate. Furthermore, to ensure sufficient pickup capability even for extremely thin wafers, for example, two- or three-stage thrusting may be used. Furthermore, the semiconductor chip 60 with adhesive layer piece attached may be picked up using a method other than the method using the suction collet 74.

<Semiconductor chip bonding process>
In this step, the picked-up semiconductor chip 60 with adhesive layer piece is bonded to the support member 80 via the adhesive layer piece 10a by thermocompression bonding (see FIG. 3(f)). A plurality of semiconductor chips 60 with adhesive layer piece may be bonded to the support member 80.

The heating temperature during thermocompression bonding may be, for example, 80 to 160°C. The load during thermocompression bonding may be, for example, 5 to 15 N. The heating time during thermocompression bonding may be, for example, 0.5 to 20 seconds.

<Thermosetting process>
In this process, the adhesive layer piece 10a of the semiconductor chip 60 with the adhesive layer piece bonded to the support member 80 is thermally cured. By (further) thermally curing the adhesive layer piece 10a or the cured adhesive layer piece 10ac that bonds the semiconductor chip Wa to the support member 80, a stronger adhesive fixation is possible. Furthermore, (further) thermally curing the adhesive layer piece 10a or the cured adhesive layer piece 10ac tends to make it easier to obtain a sintered body of component (a). When performing thermal curing, pressure may be applied simultaneously to harden the adhesive layer piece 10a. The heating temperature in this process can be appropriately adjusted depending on the constituent components of the adhesive layer piece 10a. The heating temperature may be, for example, 60 to 200°C, 90 to 190°C, or 120 to 180°C. The heating time may be 30 minutes to 5 hours, 1 to 3 hours, or 2 to 3 hours. The temperature or pressure may be changed stepwise.

The adhesive layer piece 10a can be hardened through a semiconductor chip bonding process or a thermal curing process to become the cured adhesive layer piece 10ac. The cured adhesive layer piece 10ac can contain a sintered body of component (a). Therefore, the resulting semiconductor device can have excellent heat dissipation properties.

The method for manufacturing a semiconductor device may, as necessary, include a process (wire bonding process) in which the tip of the terminal portion (inner lead) of the support member is electrically connected to the electrode pad on the semiconductor chip with a bonding wire. Examples of bonding wires that can be used include gold wire, aluminum wire, and copper wire. The temperature used for wire bonding may be within the range of 80 to 250°C or 80 to 220°C. The heating time may be from a few seconds to a few minutes. Wire bonding may be performed using a combination of ultrasonic vibration energy and compression energy from applied pressure while the material is heated within the above temperature range.

The method for manufacturing a semiconductor device may, if necessary, include a step of encapsulating the semiconductor chip with an encapsulant (encapsulation step). This step is performed to protect the semiconductor chip or bonding wires mounted on the support member. This step can be performed by molding the encapsulating resin (encapsulation resin) in a mold. The encapsulating resin may be, for example, an epoxy-based resin. The heat and pressure used during encapsulation bury the support member and residue, preventing peeling due to air bubbles at the adhesive interface.

The method for manufacturing a semiconductor device may, if necessary, include a step (post-curing step) to completely cure any encapsulating resin that was not sufficiently cured during the encapsulating step. Even if the adhesive layer pieces are not thermally cured during the encapsulating step, this step allows the adhesive layer pieces to be thermally cured along with the curing of the encapsulating resin, thereby enabling adhesive fixation. The heating temperature in this step can be set appropriately depending on the type of encapsulating resin, and may be, for example, within the range of 165 to 185°C, and the heating time may be approximately 0.5 to 8 hours.

The method for manufacturing a semiconductor device may, if necessary, include a step of heating the semiconductor chip with the adhesive layer attached to the support member using a reflow furnace (heating and melting step). In this step, the resin-encapsulated semiconductor device may be surface-mounted on the support member. Examples of surface-mounting methods include reflow soldering, in which solder is first supplied onto a printed wiring board, then heated and melted using hot air or the like to perform soldering. Examples of heating methods include hot air reflow and infrared reflow. Furthermore, the heating method may be to heat the entire surface or to heat localized areas. The heating temperature may be, for example, within the range of 240 to 280°C.

Figure 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 200 shown in Figure 4 includes a semiconductor chip Wa, a support member 80 on which the semiconductor chip Wa is mounted, and an adhesive member 12. The adhesive member 12 is provided between the semiconductor chip Wa and the support member 80 and bonds the semiconductor chip Wa to the support member 80. The adhesive member 12 is a cured product of the die bonding film (cured product 10ac of the adhesive layer piece). The connection terminals (not shown) of the semiconductor chip Wa may be electrically connected to external connection terminals (not shown) via wires 70. The semiconductor chip Wa may be encapsulated by an encapsulant layer 92 formed from an encapsulant. Solder balls 94 may be formed on the surface of the support member 80 opposite the surface 80A for electrical connection to an external substrate (motherboard) (not shown).

The semiconductor chip Wa may be, for example, an IC (integrated circuit). Examples of the support member 80 include lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resin and epoxy resin; modified plastic films made by impregnating and curing plastics such as polyimide resin and epoxy resin into glass nonwoven fabric; and ceramics such as alumina.

The semiconductor device 200 has excellent heat dissipation properties because it uses the cured die bonding film as the adhesive member.

The present disclosure will be explained in detail below based on examples, but the present disclosure is not limited to these.

(Example 1 and Comparative Examples 1 and 2)
[Preparation of die bonding film]
<Preparation of adhesive varnish>
A raw varnish was prepared by adding cyclohexanone as an organic solvent to components (a), (b) or (b'), (c), (d), and (e) according to the symbols and compositional ratios (unit: parts by mass) shown in Table 1. The raw varnish was stirred at 4,000 rpm for 20 minutes using a Homodisper (T.K. HOMO MIXER MARK II, manufactured by Tajima Chemical Machinery Co., Ltd.) at a mixing temperature of 70°C. The raw varnish was then allowed to cool to 20-30°C, after which components (f) and (g) were added to the raw varnish and stirred overnight at 250 rpm using a Three-One motor. In this manner, adhesive varnishes of Example 1 and Comparative Examples 1 and 2 were prepared, each containing 61-62% by mass of components (a), (b) or (b'), (c), (d), (e), (f), and (g).

The symbols for each component in Table 1 have the following meanings:

Component (a): Silver-containing particles produced by a reduction method (silver-containing particles surface-treated (coated) with a surface treatment agent)
(a-1) Silver particles AG-3-1F (trade name, manufactured by Dowa Electronics Co., Ltd., shape: spherical, average particle size (laser 50% particle size (D ₅₀ )): 1.4 μm)

Component (b): Compound (b-1) represented by formula (1) 2-methylglutaric acid

Component (b'): Compound other than the compound represented by formula (1) (b'-1) 3-methylglutaric acid
(b'-2) 3,3-tetramethylene glutaric acid

Component (c): Thermosetting resin (c-1) N-500P-10 (trade name, manufactured by DIC Corporation, cresol novolac epoxy resin, epoxy equivalent: 204 g/eq, softening point: 84°C)
(c-2) EXA-830CRP (trade name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 159 g/eq, liquid at 25°C)

Component (d): Curing agent (d-1) MEH-7800M (trade name, manufactured by Meiwa Kasei Co., Ltd. (now UBE Corporation), phenylaralkyl phenolic resin, hydroxyl group equivalent: 174 g/eq, softening point: 80°C)

Component (e): Elastomer (e-1) SG-P3 solvent-changed product (trade name, manufactured by Nagase ChemteX Corporation, acrylic rubber, weight-average molecular weight: 800,000, Tg: 12°C)

Component (f): Curing accelerator (f-1) 1B2MZ (trade name, manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-methylimidazole)

Component (g): Coupling agent (g-1) Z-6119 (trade name, manufactured by Dow-Toray Industries, Inc., 3-ureidopropyltriethoxysilane)

<Preparation of die bonding film>
Die-bonding films were produced using each of the adhesive varnishes described above. Each adhesive varnish was vacuum degassed, and then coated onto a support film, a polyethylene terephthalate (PET) film (thickness: 38 μm) that had been subjected to a release treatment. The coated adhesive varnish was heated and dried in two stages at different temperatures, first at 90°C for 5 minutes and then at 130°C for 5 minutes, to obtain die-bonding films of Example 1 and Comparative Examples 1 and 2, each having a thickness of 25 μm, in a B-stage state on the support film.

<Calculation of volume percent>
The content (volume %) of the component (a) was calculated from the following formula (I) using the density of the die bonding film as x (g/cm ³ ), the density of the component (a) as y (g/cm ³ ), and the mass proportion of the component (a) in the die bonding film as z (mass %). The mass proportion of the component (a) in the die bonding film was determined by thermogravimetric analysis using a thermogravimetric differential thermal analyzer (TG-DTA). The densities of the die bonding film and the component (a) were determined by measuring the mass and specific gravity using a hydrometer.
(a) Component content (volume %) = (x/y) × z (I)
TG-DTA measurement conditions: temperature range 30 to 600°C (heating rate 30°C/min), maintained at 600°C for 20 minutes; air flow rate: 300 mL/min; thermogravimetric differential thermal analyzer: TG/DTA220, manufactured by Seiko Instruments Inc.
Hydrometer: Alpha Mirage Co., Ltd., EW-300SG

[Evaluation of die bonding film (measurement of thermal conductivity)]
(Preparation of film for measuring thermal conductivity)
The die bonding film was cut to a predetermined size, and eight film pieces (thickness: 25 μm) were prepared for Example 1 and Comparative Examples 1 and 2. These film pieces were then laminated using a rubber roll on a hot plate at 70°C to prepare a laminate with a thickness of 200 μm. Each laminate was then thermally cured at 170°C for 3 hours in a clean oven (manufactured by Espec Corporation) to obtain a sample in a C-stage state. The prepared sample was cut into 1 cm x 1 cm pieces, and this was used as a film for measuring thermal conductivity. Thermal conductivity was measured under the following measurement items/conditions. The results are shown in Table 1. The values shown in Table 1 are relative values when the thermal conductivity value of Comparative Example 1 is set to 100.

(Calculation of thermal conductivity)
The thermal conductivity λ of the film for measuring thermal conductivity in the thickness direction was calculated by the following formula.
Thermal conductivity λ (W/(m・K)) = Thermal diffusivity α (m ² /s) × Specific heat Cp (J/(kg・K)) × Density ρ (g/cm ³ )
The thermal diffusivity α, specific heat Cp, and density ρ were measured by the following methods: A high thermal conductivity λ means that the semiconductor device has better heat dissipation properties.

(Measurement of thermal diffusivity α)
A measurement sample was prepared by blackening both sides of a thermal conductivity measurement film with graphite spray. The thermal diffusivity α of the measurement sample was determined by the laser flash method (xenon flash method) using the following measuring device under the following conditions.
Measurement device: Thermal diffusivity measurement device (manufactured by Netsch Japan Co., Ltd., product name: LFA447 nanoflash)
Pulse width of pulsed light irradiation: 0.1 ms
・Applied voltage for pulsed light irradiation: 236V
・Measurement sample treatment: Both sides of the thermal conductivity measurement film are blackened with graphite spray. ・Measurement ambient temperature: 25°C ± 1°C

(Measurement of specific heat Cp (25°C))
The specific heat Cp (25° C.) of the film for measuring thermal conductivity was determined by differential scanning calorimetry (DSC) using the following measuring device under the following conditions.
Measurement device: differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., product name: Pyris1)
Reference material: sapphire Heating rate: 10°C/min Heating temperature range: room temperature (25°C) to 60°C

(Measurement of density ρ)
The density ρ of the film for measuring thermal conductivity was measured by the Archimedes method using the following measuring device under the following conditions.
Measuring device: Electronic hydrometer (manufactured by Alpha Mirage Co., Ltd., product name: SD200L)
・Water temperature: 25℃

As shown in Table 1, the die bonding film of Example 1, which contains the compound represented by formula (1), was superior in thermal conductivity to the die bonding films of Comparative Examples 1 and 2, which do not contain the compound represented by formula (1). These results confirm that the integrated dicing and die bonding film of the present disclosure can be used to manufacture semiconductor devices with excellent heat dissipation properties.

10...adhesive layer, 10A...die bonding film, 10a...adhesive layer piece, 10ac...cured adhesive layer piece, 12...adhesive member, 20...support film, 30, 30a...pressure-sensitive adhesive layer, 40...substrate layer, 50...dicing tape, 60...semiconductor chip with adhesive layer piece, 70...wire, 72...needle, 74...suction collet, 80...support member, 92...sealant layer, 94...solder ball, 100...integrated dicing and die bonding film, 200...semiconductor device, W...semiconductor wafer, Wa...semiconductor chip.

Claims (14)

A first step of preparing a raw material varnish containing silver-containing particles produced by a reduction method, a compound represented by formula (1), and an organic solvent;
a second step of mixing the raw varnishes to obtain an adhesive varnish;
a third step of applying the adhesive varnish to a support film and removing the organic solvent to obtain a die-bonding film;
Equipped with
the content of the silver-containing particles is 70 mass% or more based on the total solid content of the adhesive varnish;
A method for manufacturing a die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.] a first step of preparing a raw varnish containing silver-containing particles surface-treated with a surface treatment agent, a compound represented by formula (1), and an organic solvent;
a second step of mixing the raw varnishes to obtain an adhesive varnish;
a third step of applying the adhesive varnish to a support film and removing the organic solvent to obtain a die-bonding film;
Equipped with
the content of the silver-containing particles is 70 mass% or more based on the total solid content of the adhesive varnish;
A method for manufacturing a die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.] The second step is a step of mixing the raw varnishes under a temperature condition of 50°C or higher.
A method for producing the die bonding film according to claim 1 or 2. The raw varnish further contains a thermosetting resin, a curing agent, and an elastomer.
A method for producing the die bonding film according to claim 1 or 2. The thermosetting resin includes an epoxy resin that is liquid at 25°C.
The method for producing the die bonding film according to claim 4. the second step is a step of adding a thermosetting resin, a curing agent, and an elastomer to the mixed raw varnish to obtain an adhesive varnish further containing these;
A method for producing the die bonding film according to claim 1 or 2. The thermosetting resin includes an epoxy resin that is liquid at 25°C.
The method for producing the die bonding film according to claim 6. preparing a dicing tape having a base layer and an adhesive layer provided on the base layer;
a step of bonding a die bonding film manufactured by the die bonding film manufacturing method according to claim 1 or 2 to the pressure-sensitive adhesive layer of the dicing tape to form an adhesive layer made of the die bonding film on the pressure-sensitive adhesive layer;
Equipped with
A manufacturing method for integrated dicing and die bonding film. a step of attaching the adhesive layer of the dicing and die bonding integrated film manufactured by the manufacturing method of the dicing and die bonding integrated film according to claim 8 to a semiconductor wafer;
singulating the semiconductor wafer and the adhesive layer;
picking up the semiconductor chip with the adhesive layer piece from the dicing tape;
a step of adhering the semiconductor chip with the adhesive layer piece to a support member via the adhesive layer piece;
Equipped with
A method for manufacturing a semiconductor device. The silver-containing particles are produced by a reduction method, and the compound is represented by formula (1),
The content of the silver-containing particles is 70 mass% or more based on the total amount of the die bonding film.
Die bonding film.
In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.
However, at least one of R ¹ , R ² , R ³ , and R ⁴ is a halogen atom, a methyl group optionally substituted with a halogen atom, or an ethyl group optionally substituted with a halogen atom.] Further containing a thermosetting resin, a curing agent, and an elastomer.
The die bonding film according to claim 10. The thermosetting resin includes an epoxy resin that is liquid at 25°C.
The die bonding film according to claim 11 . a dicing tape having a base layer and a pressure-sensitive adhesive layer provided on the base layer;
An adhesive layer made of the die bonding film according to any one of claims 10 to 12, which is placed on the pressure-sensitive adhesive layer of the dicing tape;
Equipped with
Integrated dicing and die bonding film. A semiconductor chip;
a support member on which the semiconductor chip is mounted;
an adhesive member provided between the semiconductor chip and the support member, the adhesive member bonding the semiconductor chip and the support member;
Equipped with
The adhesive member comprises a cured product of the die bonding film according to any one of claims 10 to 12.
Semiconductor device.