Film-like adhesive and method for manufacturing the same, dicing-die bonding integrated film, and semiconductor device and method for manufacturing the same

Abstract

Disclosed is a film-like adhesive. The film-like adhesive contains metal particles, a thermosetting resin, a setting agent, and an elastomer. The average diameter (D50) of the metal particles is 1.0-2.5 μm. A manufacturing method for the film-like adhesive is also disclosed. The manufacturing method for the film-like adhesive comprises a step for preparing an adhesive varnish by mixing a starting material varnish containing metal particles, a thermosetting resin, a setting agent, an elastomer, and an organic solvent at a mixing temperature of 50°C or higher, and a step for using the adhesive varnish to form a film-like adhesive.

Description

[Technical Field]

[0001] This disclosure relates to a film-like adhesive and a method for manufacturing the same, a dicing-die bonding integrated film, and a semiconductor device and a method for manufacturing the same. [Background technology]

[0002] Conventionally, 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 individual semiconductor chips (dicing process). Subsequently, a pickup process, a crimping process, and a die bonding process are carried out. Patent Document 1 discloses an adhesive film (dicing / die bonding integrated film) that has 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. By separating the semiconductor wafer and the adhesive layer in the dicing process, semiconductor chips with adhesive pieces can be obtained.

[0003] In recent years, devices called power semiconductor devices, which control power and perform other functions, have become widespread. Power semiconductor devices tend to generate heat due to the supplied current, and therefore require excellent heat dissipation. Patent document 2 discloses a film-like adhesive that has higher heat dissipation after curing than before curing. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-218571 [Patent Document 2] Japanese Patent Publication No. 2016-103524 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Incidentally, with the miniaturization of semiconductor devices, film-type adhesives are required to have excellent heat dissipation properties and to be thin (for example, 30 μm or less). However, conventional film-type adhesives do not achieve high levels of both heat dissipation and thin-film formation, and there is still room for improvement.

[0006] Therefore, the main objective of this disclosure is to provide a film-like adhesive that can be used to manufacture semiconductor devices with excellent heat dissipation properties and can also be made into a thin film. [Means for solving the problem]

[0007] In order to solve the above problem, the inventors of this disclosure have developed an average particle size (D) of metal particles. 50 Upon diligent investigation focusing on ), we found that a film-like adhesive has a predetermined average particle size (D 50 By using metal particles having the properties described above, we discovered that heat dissipation is improved and thin films can be created, thus completing the invention of this disclosure.

[0008] One aspect of this disclosure relates to a film-like adhesive. The film-like adhesive contains metal particles, a thermosetting resin, a curing agent, and an elastomer. The average particle size of the metal particles (D 50 The thickness is 1.0 to 2.5 μm. The film adhesive of this disclosure provides a film adhesive that can be used to manufacture semiconductor devices with excellent heat dissipation properties and can be made into thin films.

[0009] In one embodiment of the film-type adhesive, the content of metal particles is 74.0% by mass or more, based on the total amount of metal particles, thermosetting resin, curing agent, and elastomer. In another embodiment of the film-type adhesive, the content of metal particles is 24.0% by volume or more, based on the total amount of metal particles, thermosetting resin, curing agent, and elastomer. The total content of thermosetting resin and curing agent may be 13.0% by mass or more, based on the total amount of metal particles, thermosetting resin, curing agent, and elastomer.

[0010] The thickness of the film-like adhesive may be 5 to 30 μm.

[0011] In the film-like adhesive, the thermal conductivity (25°C ± 1°C) after heat curing at 170°C for 3 hours may be 2.0 W / m·K or more.

[0012] Another aspect of the present disclosure relates to a method for manufacturing the above film-like adhesive. The method for manufacturing the film-like adhesive includes a step of mixing a raw material varnish containing metal particles, a thermosetting resin, a curing agent, an elastomer, and an organic solvent at a mixing temperature of 50°C or higher to prepare an adhesive varnish, and a step of forming a film-like adhesive using the adhesive varnish.

[0013] Another aspect of the present disclosure relates to a dicing / die bonding integrated film. The dicing / die bonding integrated film includes a base material layer, an adhesive layer, and an adhesive layer made of the above film-like adhesive in this order.

[0014] Another aspect of the present disclosure relates to a semiconductor device. The semiconductor device includes a semiconductor chip, a support member on which the semiconductor chip is mounted, and an adhesive member provided between the semiconductor chip and the support member for bonding the semiconductor chip and the support member. The adhesive member is a cured product of the above film-like adhesive.

[0015] Another aspect of the present disclosure relates to a method for manufacturing a semiconductor device. The method for manufacturing the semiconductor device includes a step of attaching a semiconductor wafer to the adhesive layer of the above dicing / die bonding integrated film, a step of dicing the semiconductor wafer to which the adhesive layer is attached to produce a plurality of singulated semiconductor chips with adhesive pieces, and a step of bonding the semiconductor chips with adhesive pieces to a support member via the adhesive pieces.

Advantages of the Invention

[0016] According to the present disclosure, a semiconductor device excellent in heat dissipation can be manufactured, and a film-like adhesive capable of being thinned is provided. Further, according to the present disclosure, a dicing / die bonding integrated film using such a film-like adhesive is provided. Furthermore, according to the present disclosure, a semiconductor device using such a film-like adhesive or a dicing / die bonding integrated film and a manufacturing method thereof are provided.

Brief Description of Drawings

[0017] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an embodiment of a film-like adhesive. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an embodiment of a dicing / die bonding integrated film. [Figure 3] FIG. 3 is a schematic cross-sectional view showing an embodiment of a method for manufacturing a semiconductor device. FIGS. 3(a), (b), (c), (d), (e), and (f) are cross-sectional views schematically showing each step. [Figure 4] FIG. 4 is a schematic cross-sectional view showing an embodiment of a semiconductor device.

Embodiments for Carrying Out the Invention

[0018] Hereinafter, embodiments of the present disclosure will be described with appropriate reference to the drawings. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including steps, etc.) are not essential unless specifically stated. The sizes of the constituent elements in each figure are conceptual, and the relative size relationships between the constituent elements are not limited to those shown in each figure.

[0019] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one step in the numerical range may be replaced with the upper or lower limit of another step in the numerical range. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way. In this specification, "(meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl". Furthermore, "(poly)" means both with and without the prefix "poly". Furthermore, "A or B" means that either A or B is included, or both are included. Furthermore, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more. The content of each component in a composition refers to the total amount of any multiple substances present in the composition, unless otherwise specified.

[0020] [Film-like adhesive and method for manufacturing the same] Figure 1 is a schematic cross-sectional view showing one embodiment of a film-like adhesive. The film-like adhesive 10A shown in Figure 1 is thermosetting and undergoes a semi-cured (B stage) state before reaching a (fully) cured (C stage) state after curing treatment. The film-like adhesive 10A may be provided on a support film 20, as shown in Figure 1. The film-like adhesive 10A may be a die bonding film used for bonding a semiconductor chip to a support member or to semiconductor chips themselves.

[0021] The support film 20 is not particularly limited, but examples include films made of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, etc. The support film may be treated with a release agent. The thickness of the support film 20 may be, for example, 10 to 200 μm or 20 to 170 μm.

[0022] The film-like adhesive 10A contains metal particles (hereinafter sometimes referred to as "component (A)"), a thermosetting resin (hereinafter sometimes referred to as "component (B)"), a curing agent (hereinafter sometimes referred to as "component (C)"), and an elastomer (hereinafter sometimes referred to as "component (D)"). The film-like adhesive 10A may further contain a coupling agent (hereinafter sometimes referred to as "component (E)"), a curing accelerator (hereinafter sometimes referred to as "component (F)"), etc.

[0023] (A) Component: Metal particles (A) The metal particles as component are used to enhance heat dissipation when the film adhesive is applied to a semiconductor device.

[0024] Component (A) may be metal particles containing at least one metal selected from the group consisting of silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, lead, and titanium, or it may be metal particles containing at least one metal selected from the group consisting of silver, copper, and gold. Component (A) may be metal particles composed of one metal, or it may be metal particles composed of two or more metals. Metal particles composed of two or more metals may be metal-coated metal particles in which the surface of the metal particles is coated with a metal different from the metal particles.

[0025] (A) Component is, for example, a highly conductive metal (for example, an electrical conductivity (0°C) of 40 × 10 6It may be a conductive particle composed of a metal with an electrical conductivity of 40×10

[0026] S / m or more or a metal with a thermal conductivity (at 20°C) of 250 W / m·K or more. By using such a component (A), the heat dissipation performance can be further improved. 6 Examples of the metal with an electrical conductivity (at 0°C) of 40×10 6 S / m or more include gold (49×10 6 S / m), silver (67×10 6 S / m), copper (65×10 6 S / m), etc. The electrical conductivity (at 0°C) may be 45×10 6 S / m or more or 50×10

[0027] S / m or more. That is, the component (A) is preferably a conductive particle composed of silver and / or copper.

[0028] The component (A) may be silver particles because it is excellent in terms of electrical conductivity and thermal conductivity and is difficult to be oxidized. The silver particles may be, for example, particles composed of silver (particles composed of silver alone, silver particles) or silver-coated metal particles in which the surface of metal particles (such as copper particles) is coated with silver. Examples of the silver-coated metal particles include silver-coated copper particles, etc. The component (A) may be particles composed of silver.

[0029] The silver particles are not particularly limited, and examples include silver particles produced by a reduction method (silver particles produced by a liquid-phase (wet) reduction method using a reducing agent), silver particles produced by an atomization method, etc. The silver particles as the component (A) may be silver particles produced by a reduction method.

[0030] In liquid-phase (wet) reduction methods using reducing agents, surface treatment agents (lubricants) are usually added to control particle size and prevent aggregation and fusion. Silver particles produced by liquid-phase (wet) reduction methods using reducing agents are coated on the surface with these surface treatment agents (lubricants). Therefore, silver particles produced by reduction methods can also be described as silver particles whose surfaces have been treated with surface treatment agents. 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 oleamide (melting point: 76°C) and stearamide (melting point: 100°C); aliphatic 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 aliphatic nitrile compounds such as oleanitrile (melting point: -1°C). The surface treatment agent may have a low melting point (for example, a melting point of 100°C or less) and high solubility in organic solvents.

[0031] The shape of component (A) is not particularly limited and may be, for example, flake-like, resin-like, spherical, etc., and may be spherical. When component (A) is spherical in shape, the surface roughness (Ra) of the film-like adhesive tends to be easily improved.

[0032] The average particle size of component (A) is 1.0 to 2.5 μm. When the average particle size of component (A) is 1.0 μm or larger, it tends to prevent viscosity increase when preparing adhesive varnish, allow the desired amount of component (A) to be included in the film-like adhesive, and ensure the wettability of the film-like adhesive to the substrate, resulting in better adhesion. When the average particle size of component (A) is 2.5 μm or smaller, the film moldability is improved, and the heat dissipation due to the addition of component (A) can be further enhanced. Furthermore, when the average particle size of component (A) is 2.5 μm or smaller, the thickness of the film-like adhesive can be made thinner, allowing for higher stacking of semiconductor chips, and further preventing the occurrence of cracks in semiconductor chips due to component (A) protruding from the film-like adhesive. The average particle size of component (A) may be 1.1 μm or more, or 1.2 μm or more, and may be 2.2 μm or less, 2.0 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, or 1.6 μm or less.

[0033] In this specification, the average particle size of component (A) is defined as the particle size when its ratio (volume fraction) to the total volume of component (A) is 50% (Laser 50% particle size (D 50 )) means. Average particle size (D 50 ) can be determined by measuring a suspension of component (A) suspended in water using a laser scattering particle size analyzer (e.g., Microtrac) by laser scattering.

[0034] The content of component (A) may be 74.0% by mass or more, based on the total amount of components (A), (B), (C), and (D), and may be 74.5% by mass or more, 75.0% by mass or more, 75.5% by mass or more, or 76.0% by mass or more. When the content of component (A) is 74.0% by mass or more, based on the total amount of components (A), (B), (C), and (D), the thermal conductivity of the film adhesive can be improved, and the heat dissipation of the semiconductor device can be further improved. The content of component (A) may be, for example, 85.0% by mass or less, 84.0% by mass or less, 83.0% by mass or less, 82.0% by mass or less, 81.0% by mass or less, or 80.0% by mass or less, based on the total amount of components (A), (B), (C), and (D). If the content of component (A) is 85.0% by mass or less, based on the total amount of components (A), (B), (C), and (D), the film-like adhesive can contain the other components more sufficiently. This ensures the wettability of the film-like adhesive to the substrate, resulting in better adhesion.

[0035] The content of component (A) may be 24.0% by volume or more, based on the total amount of components (A), (B), (C), and (D), and may be 24.5% by volume or more, 25.0% by volume or more, 25.5% by volume or more, or 26.0% by volume or more. When the content of component (A) is 24.0% by volume or more, based on the total amount of components (A), (B), (C), and (D), the thermal conductivity of the film adhesive can be improved, and the heat dissipation of the semiconductor device can be further improved. The content of component (A) may be, for example, 33.0% by volume or less, 31.0% by volume or less, 30.0% by volume or less, 29.0% by volume or less, or 28.0% by volume or less, based on the total amount of components (A), (B), (C), and (D). If the content of component (A) is 33.0% by volume or less, based on the total amount of components (A), (B), (C), and (D), the film-like adhesive can contain the other components more sufficiently. This ensures the wettability of the film-like adhesive to the substrate, resulting in better adhesion.

[0036] (A) The content (volume %) of component is, for example, x (g / cm³) of the density of the film adhesive. 3 ), the density of component (A) is y (g / cm³). 3 The mass percentage of component (A) in the film-like adhesive can be calculated from the following formula (I), where z (mass%) is the mass percentage of component (A) in the film-like adhesive. The mass percentage of component (A) in the film-like adhesive can be determined, for example, by performing thermogravimetric analysis using a thermogravimetric differential thermal analyzer (TG-DTA). The density of the film-like adhesive and 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 30~600°C (heating rate 30°C / min), maintain at 600°C for 20 minutes. Air flow rate: 300mL / min Thermogravimetric differential thermal analyzer: Seiko Instruments Inc., TG / DTA220 Hydrometer: EW-300SG, manufactured by Alpha Mirage Co., Ltd.

[0037] (B) Component: Thermosetting resin Component (B) is a component that hardens by forming three-dimensional bonds between molecules upon heating or other means, and exhibits adhesive properties after hardening. Component (B) may be an epoxy resin. Any epoxy resin that has epoxy groups in its molecule can be used without particular limitations. The epoxy resin may have two or more epoxy groups in its molecule.

[0038] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracenes.

[0039] The epoxy resin may include an epoxy resin with a softening point of 90°C or lower. Including an epoxy resin with a softening point of 90°C or lower tends to improve the embedding properties of the film-like adhesive because the epoxy resin liquefies sufficiently at high temperatures.

[0040] In this specification, the softening point refers to the value measured by the ring-and-ball method in accordance with JIS K7234.

[0041] The epoxy resin may include an epoxy resin that is liquid at 25°C. Including such an epoxy resin tends to improve the surface roughness (Ra) of the film-like adhesive. Examples of commercially available epoxy resins that are liquid at 25°C include EXA-830CRP (trade name, manufactured by DIC Corporation) and YDF-8170C (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0042] The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90-300 g / eq or 110-290 g / eq. When the epoxy equivalent of the epoxy resin is within this range, it tends to be easier to maintain the bulk strength of the film-like adhesive while ensuring the fluidity of the adhesive varnish when forming the film-like adhesive.

[0043] The content of component (B) may be 1.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, or 7.0% by mass or more, based on the total amount of components (A), (B), (C), and (D), and may be 15.0% by mass or less, 14.0% by mass or less, 13.0% by mass or less, 12.0% by mass or less, or 11.0% by mass or less.

[0044] (C) Ingredients: Hardener Component (C) is a component that acts as a curing agent for component (B). If component (B) is an epoxy resin, component (C) may be an epoxy resin curing agent. Examples of component (C) include phenolic resins (phenolic curing agents), acid anhydride curing agents, amine curing agents, imidazole curing agents, phosphine curing agents, azo compounds, organic peroxides, etc. If component (B) is an epoxy resin, component (C) may be a phenolic resin from the viewpoint of handling, storage stability, and curing properties.

[0045] Phenolic resins can be used without particular limitations as long as they have a phenolic hydroxyl group in their molecule. Examples of phenolic resins include novolac-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 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, and / or naphthols with dimethoxyp-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl-type phenolic resins; and phenyl aralkyl-type phenolic resins.

[0046] The phenolic resin may include a phenolic resin with a softening point of 90°C or lower. Including a phenolic resin with a softening point of 90°C or lower tends to improve the embedding properties of the film-like adhesive because the phenolic resin liquefies sufficiently at high temperatures.

[0047] The hydroxyl group equivalent of the phenolic resin may be 40-300 g / eq, 70-290 g / eq, or 100-280 g / eq. When the hydroxyl group equivalent of the phenolic resin is 40 g / eq or higher, the storage modulus of the film adhesive tends to improve further, and when it is 300 g / eq or lower, it is possible to prevent problems caused by foaming, outgassing, etc.

[0048] The ratio of the epoxy equivalent of the epoxy resin (component B) to the hydroxyl group equivalent of the phenolic resin (component C) (epoxy equivalent of the epoxy resin (component B) / hydroxyl group equivalent of the phenolic resin (component C)) 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 from the viewpoint of curability. When the equivalent ratio is 0.30 / 0.70 or higher, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70 / 0.30 or lower, it is possible to prevent the viscosity from becoming too high and to obtain more sufficient fluidity.

[0049] The content of component (C) may be 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, or 5.0% by mass or more, based on the total amount of components (A), (B), (C), and (D), and may be 15.0% by mass or less, 14.0% by mass or less, 13.0% by mass or less, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, or 9.0% by mass or less.

[0050] The total content of component (B) and component (C) may be 13.0% by mass or more, based on the total amount of component (A), component (B), component (C), and component (D). When the total content of component (B) and component (C) is 13.0% by mass or more, based on the total amount of component (A), component (B), component (C), and component (D), the wettability of the film adhesive to the adherend can be ensured, resulting in better adhesion. The total content of component (B) and component (C) may be 13.2% by mass or more, 13.5% by mass or more, 13.7% by mass or more, 14.0% by mass or more, 14.5% by mass or more, 15.0% by mass or more, or 15.5% by mass or more, based on the total amount of component (A), component (B), component (C), and component (D). The total content of component (B) and component (C) may be 30.0% by mass or less, 27.0% by mass or less, 25.0% by mass or less, 22.0% by mass or less, 20.0% by mass or less, or 18.0% by mass or less, based on the total amount of component (A), component (B), component (C), and component (D).

[0051] (D) Ingredients: Elastomer Examples of component (D) include polyimide resin, acrylic resin, urethane resin, polyphenylene ether resin, polyetherimide resin, phenoxy resin, modified polyphenylene ether resin, etc. Component (D) is one of these resins and may be a resin having a crosslinkable functional group, or it may be an acrylic resin having a crosslinkable functional group. Here, acrylic resin means a (meth)acrylic (co)polymer containing constituent units derived from (meth)acrylate ((meth)acrylic acid ester). The acrylic resin may be a (meth)acrylic (co)polymer containing constituent units derived from (meth)acrylate having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxyl group. The acrylic resin may also be an acrylic rubber such as a copolymer of (meth)acrylate and acrylonitrile. These elastomers may be used individually or in combination of two or more.

[0052] Examples of commercially available acrylic resins include SG-P3, SG-70L, SG-708-6, WS-023 EK30, SG-280 EK23, HTR-860P-3, HTR-860P-3CSP, and HTR-860P-3CSP-3DB (all manufactured by Nagase ChemteX Corporation).

[0053] The glass transition temperature (Tg) of the elastomer as component (D) may be -50 to 50°C or -30 to 20°C. When Tg is above -50°C, the tackiness of the film-like adhesive tends to decrease, resulting in improved handling. When Tg is below 50°C, the fluidity of the adhesive varnish when forming the film-like adhesive tends to be more sufficiently ensured. Here, the Tg of the elastomer as component (D) refers to the value measured using a DSC (Differential Scanning Calorimeter) (for example, Rigaku Corporation, product name: Thermo Plus 2).

[0054] The weight-average molecular weight (Mw) of the elastomer as component (D) may be 50,000 to 1,600,000, 100,000 to 1,400,000, or 300,000 to 1,200,000. If the glass transition temperature of the elastomer as component (D) is 50,000 or higher, it tends to have better film-forming properties. If the weight-average molecular weight of component (D) is 1,600,000 or lower, it tends to have better fluidity of the adhesive varnish when forming a film-like adhesive. Here, the Mw of the elastomer as component (D) refers to the value measured by gel permeation chromatography (GPC) and converted using a calibration curve with standard polystyrene.

[0055] (D) The measuring device and conditions for measuring the Mw of the elastomer as a component are as follows, for example: Pump: L-6000 (manufactured by Hitachi, Ltd.) Column: A column consisting of Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd.), Gelpack GL-R450 (manufactured by Hitachi Chemical Co., Ltd.), and Gelpack GL-R400M (manufactured by Hitachi Chemical Co., Ltd.) (each 10.7 mm (diameter) x 300 mm) linked together in this order. Eluent: Tetrahydrofuran (hereinafter referred to as "THF") Sample: Solution prepared by dissolving 120 mg of the sample in 5 mL of THF. Flow rate: 1.75mL / min

[0056] The content of component (D) may be 15.0% by mass or less, 12.0% by mass or less, 10.0% by mass or less, or 9.0% by mass or less, based on the total amount of components (A), (B), (C), and (D). If the content of component (D) is 15.0% by mass or less, based on the total amount of components (A), (B), (C), and (D), it is possible to prevent the viscosity from becoming too high, which would reduce the dispersibility of component (A) and thus reduce heat dissipation. From the viewpoint of film processability, the lower limit of the content of component (D) may be 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, or 3.0% by mass or more, based on the total amount of components (A), (B), (C), and (D).

[0057] (E) Component: Coupling agent Component (E) may be a silane coupling agent. Examples of silane coupling agents include γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0058] (F) Ingredient: Curing accelerator Examples of component (F) include imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, from the viewpoint of reactivity, component (F) may be imidazoles and their derivatives.

[0059] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. These may be used individually or in combination of two or more.

[0060] The film-like adhesive may further contain other components. Examples of other components include pigments, ion capture agents, antioxidants, and so on.

[0061] The total content of component (E), component (F), and other components may be 0.005 to 10% by mass, based on the total mass of the film adhesive.

[0062] The method for producing the film-like adhesive 10A shown in Figure 1 is not particularly limited, but for example, it can be obtained by a manufacturing method comprising the steps of: mixing a raw material varnish containing at least component (A) and an organic solvent to prepare an adhesive varnish containing component (A), component (B), component (C), component (D), and an organic solvent (mixing step); and forming a film-like adhesive using the adhesive varnish (forming step). The adhesive varnish may further contain component (E), component (F), other components, etc., as needed.

[0063] (Mixing process) The mixing step involves mixing a raw material varnish containing at least component (A) and an organic solvent to prepare an adhesive varnish containing component (A), component (B), component (C), component (D), and an organic solvent.

[0064] The organic solvent is not particularly limited as long as it can dissolve the 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, γ-butyrolactone, butyl carbitol acetate, and ethyl carbitol acetate; carbonate esters such as ethylene carbonate and propylene carbonate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and alcohols such as butyl carbitol and ethyl carbitol. These may be used individually or in combination of two or more. Of these, the organic solvent may be N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, butylcarbitol, ethylcarbitol, butylcarbitol acetate, ethylcarbitol acetate, or cyclohexanone, from the viewpoint of solubility and boiling point of the surface treatment agent. The concentration of solid components in the raw material varnish may be 10 to 80% by mass, based on the total mass of the raw material varnish.

[0065] The raw material varnish can be obtained, for example, by adding each component to a container used in a stirrer. In this case, the order in which each component is added is not particularly restricted and can be set as appropriate according to the properties of each component.

[0066] Mixing can be carried out by appropriately combining conventional agitators such as homodispers, three-way motors, mixing rotors, planetary mixers, and swivel mixers. The agitators may be equipped with heating equipment such as heater units that can control the temperature conditions of the raw material varnish or adhesive varnish. When a homodisperser is used for mixing, the rotation speed of the homodisperser may be 3000 revolutions per minute or more.

[0067] The mixing temperature in the mixing step is not particularly limited, but may be 50°C or higher. The mixing temperature in the mixing step may be heated using heating equipment or the like as needed. According to the inventors' studies of this disclosure, it has been found that when the mixing temperature in the mixing step is 50°C or higher, for example, when silver particles (preferably silver particles produced by a reduction method) are used, the resulting film-like adhesive may contain sintered silver particles in the C stage state. This phenomenon is more pronounced when silver particles produced by a reduction method are used as component (A). The reason for this phenomenon is not entirely clear, but the inventors of this disclosure believe it to be as follows: Silver particles (produced by a liquid-phase (wet) reduction method using a reducing agent) as component (A) are usually coated on the surface with a surface treatment agent (lubricant). Here, it is presumed that when the mixing temperature in the mixing step is 50°C or higher, the surface treatment agent coating the silver particles dissociates, making it easier to expose the silver surface (in a reduced state). Furthermore, since silver particles with exposed silver surfaces are more likely to come into direct contact with each other, it is presumed that when heated under conditions for curing the film-like adhesive, the silver particles will sinter and form a sintered body of silver particles. As a result, the film-like adhesive is thought to contain a sintered body of silver particles in the C-stage state. Note that silver particles produced by the atomization method are covered with a silver oxide film on their surface due to the characteristics of their manufacturing method. According to the inventors' studies in this disclosure, when using silver particles produced by the atomization method, it has been confirmed that even if the mixing temperature in the mixing step is 50°C or higher, the resulting film-like adhesive is less likely to contain a sintered body of silver particles in the C-stage state. The mixing temperature in the mixing step 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 in the mixing step 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 in the mixing process may be, for example, 1 minute or more, 5 minutes or more, 10 minutes or more, or 20 minutes or more, and may be 80 minutes or less, 60 minutes or less, or 40 minutes or less.

[0068] Components (B), (C), (D), (E), (F), or other components can be incorporated into the adhesive varnish at any stage according to the properties of each component. These components may be incorporated into the adhesive varnish by adding them to the raw material varnish before the mixing process, or by adding them to the adhesive varnish after the mixing process. Components (B) and (C) are preferably incorporated into the adhesive varnish by adding them to the raw material varnish before the mixing process. Component (D) may be incorporated into the adhesive varnish by adding it to the raw material varnish before the mixing process, or by adding it to the adhesive varnish after the mixing process. Components (E) and (F) are preferably incorporated into the adhesive varnish by adding them to the adhesive varnish after the mixing process. When adding to the adhesive varnish after the mixing process, mixing may be carried out after addition under temperature conditions below 50°C (for example, room temperature (25°C)). In this case, the conditions may be 0.1 to 48 hours at room temperature (25°C).

[0069] In one embodiment, the mixing step may be a step of mixing raw material varnish containing component (A), component (B), component (C), component (D), and an organic solvent at a mixing temperature of 50°C or higher to prepare an adhesive varnish containing component (A), component (B), component (C), component (D), and an organic solvent.

[0070] In this way, an adhesive varnish containing component (A), component (B), component (C), component (D), and an organic solvent can be prepared. After preparation, air bubbles in the varnish may be removed by vacuum degassing or the like.

[0071] The concentration of solid components in the adhesive varnish may be 10 to 80% by mass, based on the total mass of the adhesive varnish.

[0072] (Formation process) The forming process involves forming a film-like adhesive using an adhesive varnish. Methods for forming the film-like adhesive include, for example, applying the adhesive varnish to a support film.

[0073] Known methods can be used to apply the adhesive varnish to the support film, including, for example, the knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, and curtain coating method.

[0074] After applying the adhesive varnish to the support film, the organic solvent may be heated and dried as needed. The heating and drying process is not particularly limited as long as the conditions allow the organic solvent used to evaporate sufficiently, but for example, the heating and drying temperature may be 50 to 200°C and the heating and drying time may be 0.1 to 30 minutes. Heating and drying may be carried out in stages with different heating and drying temperatures or heating and drying times.

[0075] In this way, a film-like adhesive 10A can be obtained. The thickness of the film-like adhesive 10A can be adjusted as appropriate according to the application, but the film-like adhesive 10A of this disclosure can be made into a thin film, for example, with a thickness of 30 μm or less. The thickness of the film-like adhesive 10A may be, for example, 5 to 30 μm. The thickness of the film-like adhesive 10A may be 6 μm or more, 8 μm or more, or 10 μm or more, and may be 28 μm or less, 26 μm or less, or 25 μm or less.

[0076] The thermal conductivity (at 25°C ± 1°C) of the film-like adhesive 10A after heat curing at 170°C for 3 hours (C-stage state) may be 2.0 W / m·K or higher. A thermal conductivity of 2.0 W / m·K or higher tends to result in better heat dissipation of semiconductor devices. The thermal conductivity may also be 2.5 W / m·K or higher, 3.0 W / m·K or higher, 3.5 W / m·K or higher, 4.0 W / m·K or higher, 4.5 W / m·K or higher, 5.0 W / m·K or higher, 5.5 W / m·K or higher, or 6.0 W / m·K or higher. There is no particular upper limit to the thermal conductivity (at 25°C ± 1°C) of the film-like adhesive 10A in the C-stage state, but it may be 30 W / m·K or lower.

[0077] The thermal conductivity (25°C ± 1°C) of the film adhesive 10A after heat curing at 170°C for 3 hours (C-stage state) can be measured, for example, by the following method. First, the film adhesive is cut to a predetermined size, and a predetermined number of film pieces are prepared so that the thickness when laminated is 200 μm. For example, if a film adhesive with a thickness of 25 μm is used, 8 film pieces are prepared. If a film adhesive with a thickness of 10 μm is used, 20 film pieces are prepared. These film pieces are laminated on a 70°C hot plate using a rubber roll to prepare a laminate with a thickness of 200 μm. Next, each laminate is heat-cured in a clean oven (manufactured by ESPEC Corporation) at 170°C for 3 hours to obtain a sample in the C-stage state. The obtained sample is cut into 1 cm × 1 cm pieces, and the thermal conductivity is measured using these as thermal conductivity measurement films under the following measurement items / conditions.

[0078] (Calculation of thermal conductivity) The thermal conductivity λ in the thickness direction of the film used for thermal conductivity measurement is calculated using 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 by the following method. A high thermal conductivity λ indicates superior heat dissipation in semiconductor devices.

[0079] (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 thermal conductivity measurement film is then determined using the laser flash method (xenon flash method) under the following conditions, for example, with the following measurement apparatus. • Measuring device: Thermal diffusivity measuring device (manufactured by Netch Japan Co., Ltd., product name: LFA447 nanoflash) • Pulse width of pulsed light irradiation: 0.1 ms • Applied voltage for pulsed light irradiation: 236V • Processing of measurement samples: Both sides of the thermal conductivity measurement film are blackened with graphite spray. • Measurement ambient temperature: 25℃±1℃

[0080] (Measurement of specific heat Cp (25℃)) The specific heat Cp (25°C) of a thermal conductivity measurement film can be determined, for example, by performing differential scanning calorimetry (DSC) under the following conditions using the following measuring device. • Measurement device: Differential scanning calorimetry (manufactured by PerkinElmer Japan Co., Ltd., product name: Pyris1) • Reference material: Sapphire • Heating rate: 10°C / min • Temperature range: Room temperature (25℃) to 60℃

[0081] (Measurement of density ρ) The density ρ of the thermal conductivity measurement film is measured, for example, by the Archimedes method using the following measuring apparatus under the following conditions. • Measuring device: Electronic specific gravity meter (manufactured by Alpha Mirage Co., Ltd., product name: SD200L) ·Water temperature: 25℃

[0082] The thermal conductivity (25°C ± 1°C) of the film-like adhesive 10A after heat curing at 170°C for 3 hours (stage C) can be improved by methods such as increasing the content of component (A) (decreasing the content of components other than component (A)).

[0083] The shear viscosity of the film-like adhesive 10A at 110°C may be, for example, 30,000 Pa·s or less, 28,000 Pa·s or less, 26,000 Pa·s or less, 24,000 Pa·s or less, or 22,000 Pa·s or less, and may be 3,000 Pa·s or more, 5,000 Pa·s or more, 7,000 Pa·s or more, or 10,000 Pa·s or more.

[0084] The shear viscosity at 110°C can be measured, for example, by the following method. First, the film adhesive is cut to a predetermined size, and a predetermined number of film pieces are prepared so that the thickness when laminated is 300 μm. For example, if a film adhesive with a thickness of 25 μm is used, 12 film pieces are prepared. If a film adhesive with a thickness of 10 μm is used, 30 film pieces are prepared. These film pieces are laminated on a 70°C hot plate using a rubber roll to prepare a laminate with a thickness of 300 μm. Next, a sample is prepared by punching out the laminate with a φ9 mm punch, and the shear viscosity of the prepared sample is measured using a rotary viscoelasticity measuring device (manufactured by T.A. Instrument Japan Co., Ltd., product name: ARES-RDA) under the following measurement conditions. The measured value of the shear viscosity at 110°C is the shear viscosity at 110°C. When setting the gap, the gap is adjusted so that the load on the sample is 10 to 15 g. (Measurement conditions) Disc plate: Aluminum, 8mm diameter Measurement frequency: 1Hz Heating rate: 5°C / min Strain: 5% Measurement temperature: 35~150℃ Initial load: 100g

[0085] The loss modulus of elasticity of the film adhesive 10A at 110°C may be 200 kPa or less, 180 kPa or less, 160 kPa or less, 140 kPa or less, or 135 kPa or less, and may be 10 kPa or more, 30 kPa or more, 50 kPa or more, or 70 kPa or more.

[0086] The loss modulus at 110°C can be determined using a rotary viscoelasticity measuring device in the same manner as the shear viscosity measurement method at 110°C described above.

[0087] The shear viscosity and loss modulus at 110°C can be reduced by methods such as reducing the content of component (A) (increasing the content of components other than component (A)), increasing the ratio of the total amount of components (B) and (C) to the total amount of components (A), (B), (C), and (D), using component (B) or (C) which has a softening point of 90°C or lower, or using component (D) which has a small molecular weight.

[0088] [Dicing and die bonding integrated film and method for manufacturing the same] Figure 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 Figure 2 comprises a base layer 40, an adhesive layer 30, and an adhesive layer 10 consisting of a film-like adhesive 10A, in that order. The dicing-die bonding integrated film 100 can also be said to comprise a dicing tape 50 (dicing film) comprising a base layer 40 and an adhesive layer 30 provided on the base layer 40, and an adhesive layer 10 provided on the 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, etc. The dicing-die bonding integrated film 100 may have a support film 20 provided on the surface of the adhesive layer 10 opposite to the adhesive layer 30.

[0089] Examples of the base layer 40 in the dicing tape 50 include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. The base layer 40 may also be subjected to surface treatments such as primer application, UV treatment, corona discharge treatment, polishing, and etching, as needed.

[0090] The adhesive layer 30 in the dicing tape 50 is not particularly limited as long as it has sufficient adhesive strength to prevent semiconductor chips from scattering during dicing and low enough adhesive strength to avoid damaging the semiconductor chips during the subsequent semiconductor chip pickup process; conventionally known adhesive layers in the field of dicing tapes can be used. The adhesive layer 30 may be made of a pressure-sensitive adhesive or an ultraviolet-curing adhesive. If the adhesive layer is made of an ultraviolet-curing adhesive, the adhesiveness of the adhesive layer can be reduced by irradiation with ultraviolet light.

[0091] 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 viewpoint of economy and ease of handling of the film.

[0092] The dicing-die bonding integrated film 100 shown in Figure 2 can be obtained by a manufacturing method comprising the steps of preparing a dicing tape 50 comprising a film-like adhesive 10A and a base layer 40 and an adhesive layer 30 provided on the base layer 40, and bonding the film-like adhesive 10A and the adhesive layer 30 of the dicing tape 50. Known methods can be used for bonding the film-like adhesive 10A and the adhesive layer 30 of the dicing tape 50.

[0093] [Semiconductor device and method for manufacturing the same] Figure 3 is a schematic cross-sectional view showing one embodiment of a semiconductor device manufacturing method. Figures 3(a), (b), (c), (d), (e), and (f) are schematic cross-sectional views showing each step. The semiconductor device manufacturing method comprises the steps of: attaching a semiconductor wafer W to the adhesive layer 10 of the dicing-die bonding integrated film 100 (wafer lamination step, see Figures 3(a) and (b)); producing a plurality of individual semiconductor chips 60 with adhesive pieces by dicing the semiconductor wafer W to which the adhesive layer 10 is attached (dicing step, see Figure 3(c)); and bonding the semiconductor chips 60 with adhesive pieces to a support member 80 via adhesive pieces 10a (semiconductor chip bonding step, see Figure 3(f)). The method for manufacturing a semiconductor device may further include, as necessary, a step of irradiating the adhesive layer 30 with ultraviolet light (through the substrate layer 40) (ultraviolet irradiation step, see Figure 3(d)), a step of picking up the semiconductor chip Wa (adhesive-attached semiconductor chip 60) with adhesive pieces 10a attached from the adhesive layer 30a (pickup step, see Figure 3(e)), and a step of thermally curing the adhesive pieces 10a on the adhesive-attached semiconductor chip 60 that is attached to the support member 80 (thermal curing step).

[0094] <Wafer lamination process> In this process, first, the dicing-die bonding integrated film 100 is placed in a predetermined apparatus. Next, the surface Ws of the semiconductor wafer W is attached to the adhesive layer 10 of the dicing-die bonding integrated film 100 (see Figures 3(a) and (b)). The circuit surface of the semiconductor wafer W may be provided on the side opposite to the surface Ws.

[0095] Examples of semiconductor wafers W include single-crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.

[0096] <Dicing Process> In this process, the semiconductor wafer W and the adhesive layer 10 are diced to form individual pieces (see Figure 3(c)). At this time, a portion of the adhesive layer 30, or all of the adhesive layer 30 and a portion of the substrate layer 40, may be diced to form individual pieces. In this way, the dicing-die bonding integrated film 100 also functions as a dicing sheet.

[0097] <Ultraviolet irradiation process> If the adhesive layer 30 is an ultraviolet-curable adhesive layer, the method for manufacturing the semiconductor device may include an ultraviolet irradiation step. In this step, ultraviolet light is irradiated onto the adhesive layer 30 (through the substrate layer 40) (see Figure 3(d)). In ultraviolet irradiation, the wavelength of the ultraviolet light may be 200 to 400 nm. The ultraviolet irradiation conditions are illuminance and irradiation dose of 30 to 240 mW / cm², respectively. 2 The range and 50-500 mJ / cm 2 It may be within that range.

[0098] <Pickup Process> In this process, the substrate layer 40 is expanded to separate the individual semiconductor chips 60 with adhesive pieces attached, and the semiconductor chips 60 with adhesive pieces attached, which are pushed up from the substrate layer 40 side by the needle 72, are picked up from the adhesive layer 30a by the suction collet 74 (see Figure 3(e)). The semiconductor chip 60 with adhesive pieces attached consists of a semiconductor chip Wa and adhesive pieces 10a. The semiconductor chip Wa is an individualized semiconductor wafer W, and the adhesive pieces 10a are individualized adhesive layers 10. The adhesive layer 30a is an individualized adhesive layer 30. The adhesive layer 30a may remain on the substrate layer 40 after the semiconductor chips 60 with adhesive pieces attached are picked up. In this process, it is not always necessary to expand the substrate layer 40, but expanding the substrate layer 40 can further improve the pick-up performance.

[0099] The amount of upward thrust by the needle 72 can be set as appropriate. Furthermore, from the viewpoint of ensuring sufficient pickup even for ultrathin wafers, for example, two or three stages of upward thrust may be performed. In addition, the semiconductor chip 60 with adhesive residue may be picked up by a method other than the method using the suction collet 74.

[0100] <Semiconductor chip bonding process> In this process, the picked-up semiconductor chip 60 with adhesive piece attached is bonded to the support member 80 via the adhesive piece 10a by thermocompression bonding (see Figure 3(f)). Multiple semiconductor chips 60 with adhesive pieces attached may be bonded to the support member 80.

[0101] The heating temperature in the heat-sealing process may be, for example, 80 to 160°C. The load in the heat-sealing process may be, for example, 5 to 15 N. The heating time in the heat-sealing process may be, for example, 0.5 to 20 seconds.

[0102] <Thermosetting process> In this step, the adhesive piece 10a on the semiconductor chip 60 with the adhesive piece attached to the support member 80 is heat-cured. By (further) heat-curing the adhesive piece 10a or the cured product 10ac of the adhesive piece that is bonding the semiconductor chip Wa and the support member 80, stronger adhesion and fixation becomes possible. Also, if component (A) is silver particles (preferably silver particles produced by a reduction method), by (further) heat-curing the adhesive piece 10a or the cured product 10ac of the adhesive piece, it tends to be easier to obtain a sintered body of silver particles. When performing heat curing, pressure may be applied simultaneously to cure it. The heating temperature in this step can be appropriately changed depending on the components of the adhesive 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. Note that the temperature or pressure may be changed in stages.

[0103] The adhesive piece 10a can be cured by going through a semiconductor chip bonding process or a thermosetting process to become a cured adhesive piece 10ac. If component (A) is silver particles (preferably silver particles produced by a reduction method), the cured adhesive piece 10ac may contain a sintered body of silver particles. Therefore, the resulting semiconductor device may have excellent heat dissipation properties.

[0104] A method for manufacturing a semiconductor device may, if necessary, include a step (wire bonding step) of electrically connecting the tip of the terminal portion (inner lead) of a support member to the electrode pad on the semiconductor element with a bonding wire. Examples of bonding wires include gold wire, aluminum wire, copper wire, etc. The temperature during wire bonding may be in the range of 80 to 250°C or 80 to 220°C. The heating time may be several seconds to several minutes. Wire bonding may be performed by a combination of ultrasonic vibration energy and applied pressure to create a bond while heated within the above temperature range.

[0105] A method for manufacturing a semiconductor device may optionally include a step of sealing a semiconductor element with a sealing material (sealing step). This step is performed to protect the semiconductor element or bonding wire mounted on a support member. This step can be performed by molding a sealing resin (sealing resin) in a mold. The sealing resin may be, for example, an epoxy resin. The heat and pressure during sealing embed the support member and residue, preventing delamination due to air bubbles at the adhesive interface.

[0106] The method for manufacturing a semiconductor device may, if necessary, include a step (post-curing step) to completely cure the sealing resin that is not sufficiently cured in the sealing step. Even if the adhesive piece is not heat-cured in the sealing step, in this step, the adhesive piece can be heat-cured along with the curing of the sealing resin, enabling adhesive fixation. The heating temperature in this step can be appropriately set depending on the type of sealing resin, and may be in the range of 165 to 185°C, for example, and the heating time may be about 0.5 to 8 hours.

[0107] The method for manufacturing a semiconductor device may, if necessary, include a step (heating and melting step) of heating the semiconductor element with adhesive pieces attached to a support member using a reflow oven. 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 supplied onto a printed circuit board in advance, then heated and melted with hot air or the like to perform soldering. Examples of heating methods include hot air reflow and infrared reflow. Furthermore, the heating method may involve heating the entire device or heating only a specific area. The heating temperature may be, for example, in the range of 240 to 280°C.

[0108] Figure 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 200 shown in Figure 4 comprises 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 adheres the semiconductor chip Wa and the support member 80. The adhesive member 12 is a cured product of a film-like adhesive (cured adhesive piece 10ac). 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 sealed by a sealing layer 92 formed from a sealing material. Solder balls 94 may be formed on the surface of the support member 80 opposite to the surface 80A for electrical connection to an external substrate (motherboard) (not shown).

[0109] The semiconductor chip Wa (semiconductor element) 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 obtained by impregnating and curing a substrate such as glass nonwoven fabric with plastic such as polyimide resin and epoxy resin; and ceramics such as alumina.

[0110] The semiconductor device 200 has excellent heat dissipation properties because it includes a cured product of the above-mentioned film-like adhesive as an adhesive member. [Examples]

[0111] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0112] (Examples 1-5 and Comparative Examples 1 and 2) <Preparation of adhesive varnish> The raw material varnish was prepared by adding cyclohexanone as an organic solvent to components (A), (B), (C), and (D) in the symbols and composition ratios (unit: parts by mass) shown in Table 1. The raw material varnish was stirred at 4000 rpm for 20 minutes at a mixing temperature of 70°C using a homodisper (TKHOMO MIXER MARK II, manufactured by Tajima Chemical Machinery Co., Ltd.) to obtain an adhesive varnish. Next, the adhesive varnish was left to stand until it reached 20-30°C, after which components (E) and (F) were added to the adhesive varnish and stirred overnight at 250 rpm using a three-one motor. In this way, adhesive varnishes for Examples 1-5 and Comparative Examples 1 and 2 were prepared, with a total content of components (A), (B), (C), and (D) of 61% by mass.

[0113] The symbols for each component in Table 1 mean the following:

[0114] (A) Component: Metal particles (A-1) Silver particles AG-5-1F (product name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (50% particle size of laser (D 50 )):2.9μm) (A-2) Silver particles AG-4-1F (product name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (50% particle size of laser (D 50 )):2.0μm) (A-3) Silver particles AG-3-1F (product name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (50% particle size of laser (D 50 )): 1.4μm) (A-4) Silver particles AG-2-1C (product name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (50% particle size of laser (D 50 )):0.8μm)

[0115] (B) Component: Thermosetting resin (B-1) N-500P-10 (Product name, manufactured by DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent: 204 g / eq, softening point: 84°C) (B-2) EXA-830CRP (product name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 159 g / eq, liquid at 25°C)

[0116] (C) Ingredients: Hardener (C-1) MEH-7800M (product name, manufactured by Meiwa Chemical Co., Ltd., phenyl aralkyl type phenolic resin, hydroxyl group equivalent: 174 g / eq, softening point: 80°C)

[0117] (D) Ingredients: Elastomer (D-1) HTR-860P-3CSP (Product name, manufactured by Nagase ChemteX Corporation, acrylic rubber, weight-average molecular weight: 800,000, Tg: -7℃)

[0118] (E) Component: Coupling agent (E-1)Z-6119 (product name, manufactured by Dow Toray Corporation, 3-ureidopropyltriethoxysilane)

[0119] (F) Ingredient: Curing accelerator (F-1)2PZ-CN (product name, manufactured by Shikoku Chemicals, Inc., 1-cyanoethyl-2-phenylimidazole)

[0120] <Preparation of film-like adhesives> Film-like adhesives were prepared using each of the above adhesive varnishes. Each adhesive varnish was degassed under vacuum, and the adhesive varnish was then applied to a release-treated polyethylene terephthalate (PET) film (thickness: 38 μm) which served as a support film. The applied adhesive varnish was heated and dried in two stages: 90°C for 5 minutes, followed by 130°C for 5 minutes. This yielded the film-like adhesives of Examples 1, 3-5 and Comparative Examples 1 and 2, with a thickness of 25 μm, and the film-like adhesive of Example 2, with a thickness of 10 μm, both in the B-stage state, on the support film.

[0121] <Calculation of volume percentage> (A) The content (volume %) of component is calculated by x (g / cm³) of the density of the film adhesive. 3 ), the density of component (A) is y (g / cm³). 3 The mass percentage of component (A) in the film-like adhesive was calculated from the following formula (I), where z (mass%) is the mass percentage of component (A). The mass percentage of component (A) in the film-like adhesive was determined by thermogravimetric analysis using a thermogravimetric differential thermal analyzer (TG-DTA). The density of the film-like adhesive and component (A) was 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 30~600°C (heating rate 30°C / min), maintain at 600°C for 20 minutes. Air flow rate: 300mL / min Thermogravimetric differential thermal analyzer: Seiko Instruments Inc., TG / DTA220 Hydrometer: EW-300SG, manufactured by Alpha Mirage Co., Ltd.

[0122] <Measurement of thermal conductivity> (Preparation of films for thermal conductivity measurement) The film-like adhesive was cut to a predetermined size, and eight film pieces were prepared for Examples 1, 3-5 and Comparative Examples 1 and 2 (thickness: 25 μm), and twenty film pieces were prepared for Example 2 (thickness: 10 μm). These film pieces were then laminated on a 70°C hot plate using a rubber roll to prepare laminates with a thickness of 200 μm. Next, each laminate was heat-cured in a clean oven (manufactured by ESPEC Corporation) at 170°C for 3 hours to obtain samples in the C stage. The prepared samples were cut into 1 cm × 1 cm pieces, and the thermal conductivity was measured using these as films for thermal conductivity measurement under the following measurement items / conditions. The results are shown in Table 1.

[0123] (Calculation of thermal conductivity) The thermal conductivity λ in the thickness direction of the film used for thermal conductivity measurement was calculated using the following formula. The results are shown in Table 1. 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 using the following method. A high thermal conductivity λ indicates superior heat dissipation in semiconductor devices.

[0124] (Measurement of thermal diffusivity α) Measurement samples were prepared by blackening both sides of a thermal conductivity measurement film with graphite spray. The thermal diffusivity α of the thermal conductivity measurement film was determined using the laser flash method (xenon flash method) under the following conditions and with the following measurement equipment. • Measuring device: Thermal diffusivity measuring device (manufactured by Netch Japan Co., Ltd., product name: LFA447 nanoflash) • Pulse width of pulsed light irradiation: 0.1 ms • Applied voltage for pulsed light irradiation: 236V • Processing of measurement samples: Both sides of the thermal conductivity measurement film are blackened with graphite spray. • Measurement ambient temperature: 25℃±1℃

[0125] (Measurement of specific heat Cp (25℃)) The specific heat Cp (25°C) of the thermal conductivity measurement film was determined by differential scanning calorimetry (DSC) using the following measuring apparatus under the following conditions. • Measurement device: Differential scanning calorimetry (manufactured by PerkinElmer Japan Co., Ltd., product name: Pyris1) • Reference material: Sapphire • Heating rate: 10°C / min • Temperature range: Room temperature (25℃) to 60℃

[0126] (Measurement of density ρ) The density ρ of the thermal conductivity measurement film was measured by the Archimedes method using the following measuring apparatus under the following conditions. • Measuring device: Electronic specific gravity meter (manufactured by Alpha Mirage Co., Ltd., product name: SD200L) ·Water temperature: 25℃

[0127] <Measurement of shear viscosity, storage modulus, loss modulus, and tanδ of film-like adhesives at 110°C> The film-like adhesive was cut to a predetermined size, and 12 film pieces were prepared for Examples 1, 3-5 and Comparative Examples 1 and 2 (thickness: 25 μm), and 30 film pieces were prepared for Example 2 (thickness: 10 μm). These film pieces were then laminated on a 70°C hot plate using a rubber roll to prepare laminates with a thickness of 300 μm. Next, samples were prepared by punching out each laminate with a φ9 mm punch, and the shear viscosity, storage modulus, loss modulus, and tanδ at 110°C were measured using a rotary viscoelasticity analyzer (manufactured by T.A. Instrument Japan Co., Ltd., product name: ARES-RDA) under the following measurement conditions. When setting the gap, the gap was adjusted so that the load on the sample was 10-15 g. The results are shown in Table 1. (Measurement conditions) Disc plate: Aluminum, 8mm diameter Measurement frequency: 1Hz Heating rate: 5°C / min Strain: 5% Measurement temperature: 35~150℃ Initial load: 100g

[0128] [Table 1]

[0129] In Examples 1-5 and Comparative Examples 1 and 2, it was found that film-like adhesives with a thickness of 30 μm or less could be formed. Furthermore, as shown in Table 1, the thermal conductivity was determined by the average particle size (D) of component (A). 50 The size of the metal particles has a high correlation with the average particle size (D 50 The film-like adhesives of Examples 1 to 5, which had a thickness of 1.0 to 2.5 μm, had higher thermal conductivity than the film-like adhesives of Comparative Examples 1 and 2, which did not meet this requirement. From these results, it was confirmed that the film-like adhesive of this disclosure can be used to manufacture semiconductor devices with excellent heat dissipation properties and can be made into thin films. [Explanation of Symbols]

[0130] 10...Adhesive layer, 10A...Film-type adhesive, 10a...Adhesive piece, 10ac...Cured adhesive piece, 12...Adhesive member, 20...Support film, 30,30a...Adhesive layer, 40...Base layer, 50...Dicing tape, 60...Semiconductor chip with adhesive piece, 70...Wire, 72...Needle, 74...Suction collet, 80...Support member, 92...Sealing material layer, 94...Solder ball, 100...Dicing / die bonding integrated film, 200...Semiconductor device, W...Semiconductor wafer, Wa...Semiconductor chip.

Claims

1. It contains metal particles, thermosetting resin, curing agent, and elastomer. The average particle size (D) of the metal particles ５０ ) is 1.2 to 2.5 μm. Film-type adhesive.

2. The content of the metal particles is 74.0% by mass or more, based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer. The film-like adhesive according to claim 1.

3. The content of the metal particles is 24.0% by volume or more, based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer. The film-like adhesive according to claim 1.

4. The total content of the thermosetting resin and the curing agent is 13.0% by mass or more, based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer. The film-like adhesive according to claim 2 or 3.

5. The thickness is 5 to 30 μm. A film-like adhesive according to any one of claims 1 to 4.

6. The thermal conductivity (at 25°C ± 1°C) after heat curing at 170°C for 3 hours is 2.0 W / m·K or higher. A film-like adhesive according to any one of claims 1 to 5.

7. A method for producing a film-like adhesive according to any one of claims 1 to 6, A step of preparing an adhesive varnish by mixing a raw material varnish containing the metal particles, the thermosetting resin, the curing agent, the elastomer, and an organic solvent at a mixing temperature of 50°C or higher, A step of forming a film-like adhesive using the aforementioned adhesive varnish, Equipped with, A method for manufacturing film-like adhesives.

8. The device comprises, in this order, a base layer, an adhesive layer, and an adhesive layer made of a film-like adhesive according to any one of claims 1 to 6. Dicing and die bonding integrated film.

9. Semiconductor chips and A support member on which the aforementioned semiconductor chip is mounted, An adhesive member is provided between the semiconductor chip and the support member to bond the semiconductor chip and the support member, Equipped with, A semiconductor device wherein the adhesive member is a cured product of a film-like adhesive according to any one of claims 1 to 6.

10. A step of attaching a semiconductor wafer to the adhesive layer of the dicing-die bonding integrated film according to claim 8, A step of producing a plurality of individual semiconductor chips with adhesive pieces attached by dicing the semiconductor wafer to which the adhesive layer has been attached, The process of bonding the semiconductor chip with adhesive piece to a support member via the adhesive piece, A method for manufacturing a semiconductor device, comprising:

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