Film-like adhesive, dicing / die bonding integrated film, and semiconductor device and manufacturing method thereof

Abstract

Disclosed is a film-like adhesive agent. One mode of the film-like adhesive agent contains metal particles and has a shear viscosity of 30,000 Pa•s or less at 110°C. Another mode of the film-like adhesive agent contains metal particles and has a loss modulus of 200 kPa or less at 110°C. Another mode of the film-like adhesive agent contains metal particles, a thermosetting resin, a setting agent, and an elastomer. The metal particle content is 70.0 mass% or greater, and the total of the thermosetting resin content and the setting agent content is 13.0 mass% or greater, where the total amount of the metal particles, the thermosetting resin, the setting agent, and the elastomer is used as a reference.

Description

[Technical Field]

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

[0002] Conventionally, semiconductor devices are manufactured through the following steps. First, a semiconductor wafer is attached to a dicing adhesive sheet, and in this state, the semiconductor wafer is divided into semiconductor chips (dicing step). Then, a pick-up step, a pressure-bonding step, a die-bonding step, etc. are carried out. Patent Document 1 discloses an adhesive film (a dicing / die-bonding integrated film) that has both the function of fixing a semiconductor wafer in the dicing step and the function of bonding a semiconductor chip to a substrate in the die-bonding step. In the dicing step, semiconductor chips with adhesive pieces can be obtained by dividing the semiconductor wafer and the adhesive layer into individual pieces.

[0003] In recent years, devices known as power semiconductor devices that control electric power and the like have become widespread. Power semiconductor devices are prone to generating heat due to the current supplied to them, and therefore require excellent heat dissipation properties. Patent Document 2 discloses a film-like adhesive that has higher heat dissipation properties after curing than before curing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-218571 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-103524 Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacture of semiconductor devices, film-like adhesives are required to have the ability to fill fine steps (unevenness) on a substrate. However, conventional film-like adhesives contain many metal particles to improve heat dissipation, which means that their step-filling ability is insufficient, and there is still room for improvement.

[0006] Therefore, a main object of the present disclosure is to provide a film-like adhesive that enables the production of semiconductor devices with excellent heat dissipation properties and has excellent step-filling properties. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the inventors of the present disclosure conducted an in-depth study focusing on the correlation between various parameters and step-filling ability under conditions containing metal particles, and discovered that the parameters of shear viscosity and loss modulus at 110°C are highly correlated with the quality of step-filling ability, which led to the completion of the present invention.

[0008] One aspect of the present disclosure relates to a film adhesive.

[0009] One embodiment of the film-like adhesive contains metal particles and has a shear viscosity of 30,000 Pa·s or less at 110° C. The loss modulus of the film-like adhesive at 110° C. may be 200 kPa or less.

[0010] Another embodiment of the film adhesive contains metal particles and has a loss modulus at 110°C of 200 kPa or less.

[0011] These film adhesives may further contain a thermosetting resin, a curing agent, and an elastomer, in which case the content of metal particles may be 70.0% by mass or more or 20.0% by volume or more based on the total amount of the metal particles, thermosetting resin, curing agent, and elastomer.

[0012] Another embodiment of the film-like adhesive contains metal particles, a thermosetting resin, a curing agent, and an elastomer, where the metal particle content is 70.0 mass% or more and the total content of the thermosetting resin and the curing agent is 13.0 mass% or more, based on the total amount of the metal particles, thermosetting resin, curing agent, and elastomer.

[0013] The metal particles may be conductive particles or may be silver particles.

[0014] According to the film-like adhesive of one aspect of the present disclosure, a semiconductor device with excellent heat dissipation properties can be manufactured, and the adhesive has excellent step filling properties.

[0015] Another aspect of the present disclosure relates to an integrated dicing and die bonding film, which includes, in this order, a base layer, a pressure-sensitive adhesive layer, and an adhesive layer made of the above-mentioned film-like adhesive.

[0016] 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 and adhering the semiconductor chip to the support member. The adhesive member is a cured product of the above-described film-like adhesive.

[0017] Another aspect of the present disclosure relates to a method for manufacturing a semiconductor device, comprising the steps of: attaching a semiconductor wafer to the adhesive layer of the above-mentioned dicing-die-bonding integrated film; dicing the semiconductor wafer with the adhesive layer attached to produce a plurality of individual semiconductor chips with adhesive pieces attached; and bonding the semiconductor chips with adhesive pieces to a support member via the adhesive pieces. [Effects of the Invention]

[0018] According to the present disclosure, a film-like adhesive that enables the manufacture of a semiconductor device with excellent heat dissipation properties and has excellent step-filling properties is provided. The present disclosure also provides an integrated dicing and die-bonding film using such a film-like adhesive. Furthermore, the present disclosure also provides a semiconductor device using such a film-like adhesive or dicing and die-bonding integrated film, and a method for manufacturing the same. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive. [Figure 2] FIG. 2 is a schematic cross-sectional view showing one embodiment of a dicing / die bonding integrated film. [Figure 3] 3A, 3B, 3C, 3D, 3E, and 3F are schematic cross-sectional views showing one embodiment of a method for manufacturing a semiconductor device, in which (a), (b), (c), (d), (e), and (f) are cross-sectional views showing each step. [Figure 4] FIG. 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings as appropriate. 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.

[0021] In this specification, a numerical range indicated with "to" indicates a range that includes 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 of a certain numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. Furthermore, the upper and lower limits individually described can be arbitrarily combined. Furthermore, 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)" 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, the materials exemplified below may be used alone or in combination of two or more, unless otherwise specified. When a composition contains multiple substances corresponding to each component, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.

[0022] Fig. 1 is a schematic cross-sectional view showing one embodiment of a film-like adhesive. The film-like adhesive 10A shown in Fig. 1 is thermosetting and reaches a semi-cured (B-stage) state before reaching a fully cured (C-stage) state after a curing process. The film-like adhesive 10A may be provided on a support film 20, as shown in Fig. 1. The film-like adhesive 10A may be a die-bonding film used to bond a semiconductor chip to a support member or to bond semiconductor chips to each other.

[0023] The support film 20 is not particularly limited, but examples thereof 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.

[0024] One embodiment of the film adhesive 10A contains metal particles (hereinafter sometimes referred to as "component (A)") and satisfies either condition (i) or condition (ii) below. In this case, the film adhesive may satisfy both conditions (i) and (ii). Condition (i): The shear viscosity at 110°C is 30,000 Pa·s or less. Condition (ii): The loss modulus at 110°C is 200 kPa or less.

[0025] According to studies by the inventors of the present disclosure, when a film-like adhesive contains component (A), it has been found that the parameters of shear viscosity and loss modulus of the film-like adhesive at 110°C are highly correlated with the quality of the step-filling ability. Therefore, a film-like adhesive that satisfies the above conditions can be used to manufacture semiconductor devices with excellent heat dissipation properties, and also has excellent step-filling ability.

[0026] The shear viscosity of the film-like adhesive at 110°C is 30,000 Pa·s or less, and may be 28,000 Pa·s or less, 26,000 Pa·s or less, 25,000 Pa·s or less, 24,000 Pa·s or less, 22,000 Pa·s or less, 20,000 Pa·s or less, 18,000 Pa·s or less, or 15,000 Pa·s or less. The lower limit of the shear viscosity of the film-like adhesive at 110°C is not particularly limited, but may be, for example, 3,000 Pa·s or more, 5,000 Pa·s or more, 6,000 Pa·s or more, or 7,000 Pa·s or more.

[0027] The shear viscosity at 110°C can be measured, for example, by the following method. First, a 25 μm thick film adhesive is cut to a predetermined size to prepare 12 film pieces. Next, the 12 film pieces are laminated using a rubber roll on a hot plate at 70°C to prepare a laminate with a thickness of 300 μm. Next, the laminate is punched out with a φ9 mm punch to prepare a sample. The shear viscosity of the prepared sample is measured using a rotational viscoelasticity measuring device (manufactured by TA Instruments Japan, Inc., product name: ARES-RDA) under the following measurement conditions. The measured 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

[0028] The loss modulus of the film-like adhesive at 110°C is 200 kPa or less, and may be 190 kPa or less, 180 kPa or less, 170 kPa or less, 165 kPa or less, 160 kPa or less, 155 kPa or less, 150 kPa or less, 145 kPa or less, 140 kPa or less, 135 kPa or less, 130 kPa or less, 125 kPa or less, or 120 kPa or less. The lower limit of the loss modulus of the film-like adhesive at 110°C is not particularly limited, but may be, for example, 10 kPa or more, 20 kPa or more, 30 kPa or more, 40 kPa or more, or 50 kPa or more.

[0029] The loss modulus at 110°C can be determined using a rotational viscoelasticity measuring device in the same manner as in the above-mentioned method for measuring the shear viscosity at 110°C.

[0030] The shear viscosity and loss modulus at 110°C can be reduced by, for example, decreasing the content of component (A) (increasing the content of components other than component (A)), increasing the ratio of the total amount of thermosetting resin and curing agent to the total amount of component (A), a thermosetting resin described below, a curing agent described below, and an elastomer described below, using a thermosetting resin or curing agent with a softening point of 90°C or less, or using an elastomer with a small molecular weight.

[0031] The film-like adhesive 10A may further contain 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.

[0032] (A) Component: Metal particles The metal particles as component (A) are a component that enhances heat dissipation when the film adhesive is applied to a semiconductor device.

[0033] Examples of component (A) include particles containing metals such as aluminum, nickel, tin, bismuth, indium, zinc, iron, copper, silver, gold, palladium, and platinum. Component (A) may be metal particles composed of one type of metal, or may be metal particles composed of two or more types of metal. Metal particles composed of two or more types of metal may be metal-coated metal particles in which the surface of the metal particles is coated with a metal different from the metal particles. Component (A) may be, for example, conductive particles.

[0034] The conductive particles have an electrical conductivity (0°C) of 40×10 6 The conductive particles may be metal particles made of a metal having an electrical conductivity (0°C) of 40 x 10 6 Examples of metals with a S / m or higher include gold (49×106 S / m), silver (67×10 6 S / m), copper (65×10 6 The electrical conductivity (0°C) is 45 x 10 6 S / m or more or 50 x 10 6 S / m or more. That is, the conductive particles (or metal particles as component (A)) are preferably metal particles made of silver and / or copper.

[0035] The conductive particles may be, for example, metal particles made of a metal having a thermal conductivity (20°C) of 250 W / m·K or more. The use of such conductive particles can further improve heat dissipation. Examples of metals having a thermal conductivity (20°C) of 250 W / m·K or more include gold (295 W / m·K), silver (418 W / m·K), and copper (372 W / m·K). The thermal conductivity (20°C) may be 300 W / m·K or more or 350 W / m·K or more. In other words, the conductive particles (or metal particles as component (A)) are preferably metal particles made of silver and / or copper.

[0036] Component (A) may be silver particles, which have excellent electrical conductivity and thermal conductivity and are resistant to oxidation. The silver particles may be, for example, particles composed of silver (particles composed solely of silver) or silver-coated metal particles in which the surfaces of metal particles (such as copper particles) are coated with silver. Examples of silver-coated metal particles include silver-coated copper particles. Component (A) may be particles composed of silver.

[0037] The silver particles as component (A) are not particularly limited, and examples thereof 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 component (A) may be silver particles produced by a reduction method.

[0038] In the liquid-phase (wet) reduction method using a reducing agent, a surface treatment agent (lubricant) is usually added to control particle size and prevent aggregation and fusion, and the silver particles produced by the liquid-phase (wet) reduction method using a reducing agent have their surfaces coated with a surface treatment agent (lubricant). Therefore, silver particles produced by the reduction method can also be said to be silver particles that have been surface-treated with a surface treatment agent. 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 (for example, a melting point of 100°C or less) and high solubility in organic solvents.

[0039] The shape of component (A) is not particularly limited and may be, for example, flake-like, resin-like, spherical, etc. When component (A) is spherical, the surface roughness (Ra) of the film adhesive tends to be improved.

[0040] Component (A) may be metal particles (preferably conductive particles, more preferably silver particles) with an average particle size of 0.01 to 10 μm. Metal particles with an average particle size of 0.01 μm or greater tend to provide the following effects: preventing an increase in viscosity when preparing an adhesive varnish; allowing the desired amount of metal particles to be contained in the film adhesive; and ensuring the wettability of the film adhesive to the adherend, thereby enabling better adhesion. Metal particles with an average particle size of 10 μm or less tend to provide superior film formability and further improve heat dissipation by adding metal particles. Furthermore, metal particles with an average particle size of 10 μm or less tend to allow the film adhesive to be thinner, allowing for a higher stacking density of semiconductor chips, and tend to prevent cracks in the semiconductor chips due to metal particles protruding from the film adhesive. The average particle size of the metal particles as component (A) may be 0.1 μm or more, 0.3 μm or more, or 0.5 μm or more, and may be 8.0 μm or less, 7.0 μm or less, 6.0 μm or less, 5.0 μm or less, 4.0 μm or less, or 3.0 μm or less.

[0041] In this specification, the average particle size of the metal particles as component (A) is the particle size when the ratio (volume fraction) of the total volume of the metal particles is 50% (laser 50% particle size (D 50 )) means the average particle size (D 50 ) can be determined by measuring a suspension of metal particles in water by a laser scattering method using a laser scattering particle size measuring device (for example, Microtrac).

[0042] The content of component (A) may be 70.0% by mass or more, 71.0% by mass or more, 72.0% by mass or more, 73.0% by mass or more, 74.0% by mass or more, 74.5% by mass or more, 75.0% by mass or more, or 75.5% by mass or more, based on the total amount of components (A), (B), (C), and (D). A content of component (A) of 70.0% by mass or more, based on the total amount of components (A), (B), (C), and (D), tends to improve the thermal conductivity of the film-like adhesive and further improve the heat dissipation properties of the semiconductor device. The content of component (A) may be, for example, 85.0% 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). When the content of component (A) is 85.0 mass% or less based on the total amount of components (A), (B), (C), and (D), the other components can be more sufficiently contained in the film adhesive, which makes it easier to adjust the shear viscosity and loss modulus of the film adhesive at 110°C to within specified ranges, and the film adhesive tends to have better step-filling properties.

[0043] The content of component (A) may be 20.0% by volume or more, 21.0% by volume or more, 22.0% by volume or more, 22.5% by volume or more, 23.0% by volume or more, 23.5% by volume or more, 24.0% by volume or more, 24.5% by volume or more, 24.8% by volume or more, or 25.0% by volume or more, based on the total amount of components (A), (B), (C), and (D). When the content of component (A) is 20.0% by volume or more, based on the total amount of components (A), (B), (C), and (D), the thermal conductivity of the film-like adhesive tends to be improved, and the heat dissipation properties of the semiconductor device tend to be further improved. The content of component (A) may be, for example, 33.0 vol% or less, 31.0 vol% or less, 30.0 vol% or less, or 29.0 vol% or less, based on the total amount of components (A), (B), (C), and (D). When the content of component (A) is 33.0 vol% or less, based on the total amount of components (A), (B), (C), and (D), the other components can be more sufficiently contained in the film-like adhesive. This makes it easier to adjust the shear viscosity and loss modulus of the film-like adhesive at 110°C within the specified range, and the film-like adhesive tends to have better step-filling properties.

[0044] The content (vol %) of component (A) can be determined by, for example, calculating the density of the film adhesive x (g / cm 3 ), and the density of component (A) is y (g / cm 3 ), and the mass proportion of component (A) in the film adhesive is z (mass %), it can be calculated from the following formula (I). The mass proportion of component (A) in the film adhesive can be determined by thermogravimetric analysis using, for example, a thermogravimetric differential thermal analyzer (TG-DTA). The densities of the film 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 to 600°C (heating rate 30°C / min), maintained at 600°C for 20 minutes Air flow rate: 300mL / min Thermogravimetric differential thermal analyzer: Seiko Instruments Inc., TG / DTA220 Hydrometer: Alpha Mirage EW-300SG

[0045] (B) Component: Thermosetting resin Component (B) is a component that has the property of forming three-dimensional bonds between molecules and curing when heated or the like, and is a component that exhibits adhesive properties after curing. Component (B) may be an epoxy resin. Any epoxy resin may be used without particular limitation as long as it has an epoxy group in its molecule. The epoxy resin may have two or more epoxy groups in its molecule.

[0046] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, stilbene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene.

[0047] The epoxy resin may contain an epoxy resin with a softening point of 90° C. or lower. By containing an epoxy resin with a softening point of 90° C. or lower, the epoxy resin is sufficiently liquefied at 110° C., which tends to make it easier to adjust the shear viscosity and loss modulus of the film adhesive at 110° C. to within the specified range.

[0048] In this specification, the softening point refers to a value measured by the ring and ball method in accordance with JIS K7234.

[0049] The epoxy resin may contain an epoxy resin that is liquid at 25°C. By containing such an epoxy resin as the epoxy resin, the surface roughness (Ra) of the film adhesive tends to be improved. 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, Nippon Steel Chemical & Material Co., Ltd.).

[0050] 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, the bulk strength of the film adhesive is maintained, and the fluidity of the adhesive varnish when forming the film adhesive tends to be easily ensured.

[0051] The content of component (B) may be 1.0 mass% or more, 3.0 mass% or more, 5.0 mass% or more, or 7.0 mass% or more, and may be 15.0 mass% or less, 14.0 mass% or less, 13.0 mass% or less, 12.0 mass% or less, or 11.0 mass% or less, based on the total amount of components (A), (B), (C), and (D).

[0052] Component (C): Hardener Component (C) acts as a curing agent for component (B). When component (B) is an epoxy resin, component (C) can 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, and organic peroxides. When component (B) is an epoxy resin, component (C) may be a phenolic resin from the viewpoints of handleability, storage stability, and curability.

[0053] Any phenolic resin can be used without particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenolic resin 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.

[0054] The phenolic resin may contain a phenolic resin having a softening point of 90° C. or lower. By containing a phenolic resin having a softening point of 90° C. or lower, the phenolic resin is sufficiently liquefied at 110° C., which tends to make it easier to adjust the shear viscosity and loss modulus of the film adhesive at 110° C. to within predetermined ranges.

[0055] 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-like adhesive tends to be further improved, and if it is 300 g / eq or less, it becomes possible to prevent defects due to the generation of foaming, outgassing, etc.

[0056] From the viewpoint of curability, the ratio of the epoxy equivalent of the epoxy resin (B) to the hydroxyl equivalent of the phenolic resin (C) (epoxy equivalent of the epoxy resin (B) / hydroxyl equivalent of the phenolic resin (C)) 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 the equivalent ratio is 0.30 / 0.70 or more, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70 / 0.30 or less, excessive viscosity increase can be prevented, and more sufficient fluidity can be obtained.

[0057] The content of component (C) may be 1.0 mass% or more, 3.0 mass% or more, 4.0 mass% or more, or 5.0 mass% or more, and may be 15.0 mass% or less, 12.0 mass% or less, 10.0 mass% or less, or 9.0 mass% or less, based on the total amount of components (A), (B), (C), and (D).

[0058] The combined content of components (B) and (C) may be 13.0% by mass or more, based on the combined total of components (A), (B), (C), and (D). When the combined content of components (B) and (C) is 13.0% by mass or more, based on the combined total of components (A), (B), (C), and (D), it becomes easier to adjust the shear viscosity and loss modulus of the film-like adhesive at 110°C to within a predetermined range, and the film-like adhesive tends to have better step-filling properties. The combined content of components (B) and (C) may be 13.2% by mass or more, 13.5% 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 combined total of components (A), (B), (C), and (D). The total content of the (B) component and the (C) component may be 30.0 mass% or less, 25.0 mass% or less, 23.0 mass% or less, 22.0 mass% or less, 21.0 mass% or less, 20.0 mass% or less, or 18.0 mass% or less, based on the total amount of the (A), (B), (C), and (D) components.

[0059] (D) Component: Elastomer Examples of component (D) include polyimide resins, acrylic resins, urethane resins, polyphenylene ether resins, polyetherimide resins, phenoxy resins, and modified polyphenylene ether resins. Component (D) 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 (meth)acrylic (co)polymer containing a structural unit derived from a (meth)acrylate ((meth)acrylic acid ester). The acrylic resin may be a (meth)acrylic (co)polymer containing a structural unit derived from a (meth)acrylate 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)acrylate and acrylonitrile. These elastomers may be used alone or in combination of two or more.

[0060] Commercially available acrylic resins include, for example, 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).

[0061] The glass transition temperature (Tg) of the elastomer as component (D) may be -50 to 50°C or -30 to 20°C. If the Tg is -50°C or higher, the tackiness of the film-like adhesive will be reduced, and handling will tend to be improved. If the Tg is 50°C or lower, the fluidity of the adhesive varnish when forming the film-like adhesive will tend 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, Thermo Plus 2, product name, manufactured by Rigaku Corporation).

[0062] The weight-average molecular weight (Mw) of the elastomer as component (D) may be 50,000 to 1.6 million, 100,000 to 1.4 million, or 300,000 to 1.2 million. When the glass transition temperature of the elastomer as component (D) is 50,000 or higher, the film-forming properties tend to be better. When the weight-average molecular weight of component (D) is 1.6 million or less, the fluidity of the adhesive varnish when forming a film-like adhesive tends to be better. Here, the Mw of the elastomer as component (D) means a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0063] The Mw of the elastomer as component (D) can be measured, for example, by the following device and conditions: Pump: L-6000 (Hitachi, Ltd.) Column: A column consisting of Gelpack GL-R440 (Hitachi Chemical Co., Ltd.), Gelpack GL-R450 (Hitachi Chemical Co., Ltd.), and Gelpack GL-R400M (Hitachi Chemical 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: 1.75mL / min

[0064] 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). When 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 result in a decrease in the ability to fill gaps. 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 2.8% by mass or more, based on the total amount of components (A), (B), (C), and (D).

[0065] Component (E): Coupling agent Component (E) may be a silane coupling agent, such as γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0066] (F) Component: Curing accelerator Examples of the component (F) include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. Among these, from the viewpoint of reactivity, the component (F) may be imidazoles and derivatives thereof.

[0067] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, etc. These may be used alone or in combination of two or more.

[0068] The film adhesive may further contain other components, such as pigments, ion scavengers, and antioxidants.

[0069] The total content of the component (E), the component (F), and other components may be 0.005 to 10% by mass based on the total mass of the film-like adhesive.

[0070] Another embodiment of the film-like adhesive contains component (A), component (B), component (C), and component (D). Based on the total amount of components (A), (B), (C), and (D), the content of component (A) is 74.5 mass% or more, and the total content of components (B) and (C) is 13.0 mass% or more. In the film-like adhesive of this embodiment, the type and content of each component are the same as those exemplified in the above embodiment. In addition, in the film-like adhesive of this embodiment, the preferred ranges of the shear viscosity and loss modulus at 110°C are also the same as those exemplified in the above embodiment.

[0071] [Manufacturing method of film adhesive] 1 can be produced by a method including, for example, a step of mixing a raw material varnish containing component (A) and an organic solvent to prepare an adhesive varnish containing component (A), the organic solvent, component (B), and component (C) (mixing step), and a step of forming an adhesive film using the adhesive varnish (forming step). The adhesive varnish may further contain components (D), (E), (F), and other components, as needed.

[0072] (Mixing process) The mixing step is a step of mixing a raw material varnish containing the component (A) and an organic solvent to prepare an adhesive varnish containing the component (A), the organic solvent, the component (B), and the component (C).

[0073] 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, γ-butyrolactone, butyl carbitol acetate, and ethyl carbitol acetate; carbonates 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 alone or in combination of two or more. Of these, the organic solvent may be N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, butyl carbitol, ethyl carbitol, butyl carbitol acetate, ethyl carbitol acetate, or cyclohexanone, from the viewpoint of the solubility and boiling point of the surface treatment agent. The solid component concentration in the raw varnish may be 10 to 80 mass % based on the total mass of the raw varnish.

[0074] The raw varnish can be obtained, for example, by adding each component to a container used in a mixer. In this case, the order of adding each component is not particularly limited and can be set appropriately depending on the properties of each component.

[0075] Mixing can be carried out using an appropriate combination of conventional mixers such as a Homo Disper, a Three-One Motor, a mixing rotor, a planetary rotor, or a Raikai mixer. The mixer may be equipped with a heating device such as a heater unit that can control the temperature conditions of the raw material 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.

[0076] 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 increased, if necessary, using heating equipment or the like. The inventors of the present disclosure have found that, for example, when silver particles (preferably silver particles produced by a reduction method) are used, if the mixing temperature in the mixing step is 50°C or higher, the resulting film-like adhesive may contain a sintered body of 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 the present disclosure believe it to be as follows: Silver particles (produced by a liquid-phase (wet) reduction method using a reducing agent) used as component (A) are usually coated on the surface with a surface treatment agent (lubricant). It is presumed that if the mixing temperature in the mixing step is 50°C or higher, the surface treatment agent coating the silver particles dissociates, easily exposing the silver surface (in a reduced state). Furthermore, because such silver particles with exposed silver surfaces are likely to come into direct contact with each other, it is presumed that heating the film-like adhesive under conditions that cure the silver particles will facilitate sintering and the formation of a sintered body of silver particles. This is thought to result in the film-like adhesive containing a sintered body of silver particles in a C-stage state. Silver particles produced by the atomization method are covered with a silver oxide film on their surfaces due to the characteristics of their manufacturing method. The inventors of the present disclosure have confirmed that when silver particles produced by the atomization method are used, even if the mixing temperature in the mixing step is 50°C or higher, the resulting film-like adhesive is unlikely to contain a sintered body of silver particles in a 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, 100°C or lower, or 80°C or lower. The mixing time in the mixing step may be, for example, 1 minute or more, 5 minutes or more, or 10 minutes or more, and may be 60 minutes or less, 40 minutes or less, or 20 minutes or less.

[0077] The components (B), (C), (D), (E), (F), and other components can be incorporated into the adhesive varnish at any stage, depending on the properties of each component. These components may be incorporated into the adhesive varnish by adding them to the raw varnish before the mixing step, or by adding them to the adhesive varnish after the mixing step. The components (B) and (C) are preferably incorporated into the adhesive varnish by adding them to the raw varnish before the mixing step. The component (D) may be incorporated into the adhesive varnish by adding them to the raw varnish before the mixing step, or by adding them to the adhesive varnish after the mixing step. The components (E) and (F) are preferably incorporated into the adhesive varnish by adding them to the adhesive varnish after the mixing step. When the components are added to the adhesive varnish after the mixing step, they may be mixed at a temperature below 50°C (e.g., room temperature (25°C)). In this case, the mixing conditions may be at room temperature (25°C) for 0.1 to 48 hours.

[0078] In one embodiment, the mixing step may be a step of mixing a raw material varnish containing the components (A), (B), (C), (D), and an organic solvent at a mixing temperature of preferably 50°C or higher to prepare an adhesive varnish containing the components (A), (B), (C), (D), and an organic solvent.

[0079] In this manner, an adhesive varnish containing component (A), organic solvent, component (B), and component (C) can be prepared. After preparation, air bubbles in the adhesive varnish may be removed by vacuum degassing or the like.

[0080] The solid component concentration in the adhesive varnish may be 10 to 80 mass % based on the total mass of the adhesive varnish.

[0081] (Formation process) The forming step is a step of forming a film-like adhesive using an adhesive varnish. Examples of a method for forming a film-like adhesive include a method of applying the adhesive varnish to a support film.

[0082] The adhesive varnish can be applied to the support film by any known method, such as knife coating, roll coating, spray coating, gravure coating, bar coating, or curtain coating.

[0083] After the adhesive varnish is applied to the support film, the organic solvent may be dried by heating, if necessary. The conditions for the drying by heating are not particularly limited as long as the organic solvent used is sufficiently volatilized, but for example, the drying by heating temperature may be 50 to 200°C, and the drying by heating time may be 0.1 to 30 minutes. The drying by heating may be carried out stepwise at different temperatures or for different times.

[0084] In this manner, film adhesive 10A can be obtained. The thickness of film adhesive 10A can be adjusted appropriately depending on the application, but may be, for example, 3 μm or more, 5 μm or more, or 10 μm or more, and may be 200 μm or less, 100 μm or less, 50 μm or less, or 30 μm or less.

[0085] In the C-stage state, the thermal conductivity (25°C ± 1°C) of the film-like adhesive 10A may be 1.5 W / m·K or more. A thermal conductivity of 1.5 W / m·K or more tends to improve the heat dissipation of the semiconductor device. The thermal conductivity may be 2.0 W / m·K or more, 2.5 W / m·K or more, 3.0 W / m·K or more, 3.5 W / m·K or more, 4.0 W / m·K or more, 4.5 W / m·K or more, or 5.0 W / m·K or more. The upper limit of the thermal conductivity (25°C ± 1°C) of the film-like adhesive 10A in the C-stage state is not particularly limited, but may be 30 W / m·K or less. In this specification, thermal conductivity refers to a value calculated using the method described in the Examples. Furthermore, the conditions for curing the film-like adhesive 10A to reach the C-stage state may be, for example, a heating temperature of 170°C and a heating time of 3 hours.

[0086] [Dicing and die bonding integrated film and its manufacturing method] 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 comprises, in this order, a base layer 40, a pressure-sensitive adhesive layer 30, and an adhesive layer 10 made of a film-like adhesive 10A. The dicing-die bonding integrated film 100 can also be said to comprise a dicing tape 50 comprising the base layer 40 and the pressure-sensitive adhesive layer 30 provided on the base layer 40, and an adhesive layer 10 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 comprise a support film 20 on the surface of the adhesive layer 10 opposite the pressure-sensitive adhesive layer 30.

[0087] 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. Furthermore, the base layer 40 may be subjected to surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, and etching treatment, as needed.

[0088] 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 layer conventionally known in the field of dicing tapes can be used. The adhesive layer 30 may be an adhesive layer made of a pressure-sensitive adhesive or an adhesive layer made of an ultraviolet-curing adhesive. When the adhesive layer is an adhesive layer made of an ultraviolet-curing adhesive, the adhesive property of the adhesive layer can be reduced by irradiating it with ultraviolet light.

[0089] The thickness of the dicing tape 50 (the base layer 40 and the adhesive layer 30) may be 60 to 150 μm or 70 to 130 μm from the viewpoints of economy and film handling.

[0090] 2 can be obtained by a manufacturing method including the steps of preparing a dicing tape 50 including a film adhesive 10A, a base layer 40, and a pressure-sensitive adhesive layer 30 provided on the base layer 40, and laminating the film adhesive 10A to the pressure-sensitive adhesive layer 30 of the dicing tape 50. A known method can be used to laminate the film adhesive 10A to the pressure-sensitive adhesive layer 30 of the dicing tape 50.

[0091] [Method of manufacturing a semiconductor device] 3 is a schematic cross-sectional view showing one embodiment of a method for manufacturing a semiconductor device. FIGS. 3(a), 3(b), 3(c), 3(d), 3(e), and 3(f) are cross-sectional views showing each step. The method for manufacturing a semiconductor device includes 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 FIGS. 3(a) and 3(b)); dicing the semiconductor wafer W with the adhesive layer 10 attached to it to produce a plurality of individual semiconductor chips 60 with adhesive pieces attached (dicing step, see FIG. 3(c)); and adhering the semiconductor chips 60 with adhesive pieces attached to a support member 80 via adhesive pieces 10a (semiconductor chip adhering step, see FIG. 3(f)). The method for manufacturing a semiconductor device may further include, between the dicing process and the semiconductor chip bonding process, a process of irradiating ultraviolet light onto the adhesive layer 30 (through the base layer 40) (ultraviolet light irradiation process, see Figure 3(d)), a process of picking up the semiconductor chip Wa (semiconductor chip 60 with adhesive piece) to which the adhesive piece 10a is attached from the adhesive layer 30a (pick-up process, see Figure 3(e)), and a process of thermally curing the adhesive piece 10a on the semiconductor chip 60 with adhesive piece bonded to the support member 80 (thermal curing process), as necessary.

[0092] <Wafer lamination process> In this process, first, the dicing and die bonding integrated film 100 is placed in a predetermined device. Then, the 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 surface Ws.

[0093] Examples of the semiconductor wafer W include single crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.

[0094] <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.

[0095] <Ultraviolet irradiation process> When the adhesive layer 30 is an ultraviolet-curable adhesive layer, the method for manufacturing a semiconductor device may include an ultraviolet irradiation step. In this step, ultraviolet rays are irradiated onto the adhesive layer 30 (through the base layer 40) (see FIG. 3(d)). The wavelength of the ultraviolet rays may be 200 to 400 nm. The ultraviolet irradiation conditions are an illuminance and an irradiation amount of 30 to 240 mW / cm. 2 and 50-500mJ / cm 2 may be in the range of

[0096] <Pickup process> In this process, the base layer 40 is expanded to separate the individual semiconductor chips 60 with adhesive pieces from each other, while the semiconductor chips 60 with adhesive pieces pushed up from the base layer 40 side by the needles 72 are sucked by the suction collet 74 and picked up from the adhesive layer 30a (see FIG. 3(e)). The semiconductor chips 60 with adhesive pieces have a semiconductor chip Wa and an adhesive piece 10a. The semiconductor chip Wa is obtained by dividing the semiconductor wafer W, and the adhesive 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 pieces are picked up. In this process, it is not necessarily necessary to expand the base layer 40, but expanding the base layer 40 can further improve the pick-up ability.

[0097] The amount of push-up by the needle 72 can be set as appropriate. Furthermore, from the viewpoint of ensuring sufficient pick-up capability even for ultra-thin wafers, for example, two- or three-stage push-up may be performed. Furthermore, the semiconductor chip 60 with adhesive piece attached may be picked up by a method other than the method using the suction collet 74.

[0098] <Semiconductor chip bonding process> In this step, the picked-up semiconductor chip 60 with adhesive piece is bonded to the support member 80 via the adhesive piece 10a by thermocompression bonding (see FIG. 3(f)). A plurality of semiconductor chips 60 with adhesive piece may be bonded to the support member 80.

[0099] The heating temperature in the thermocompression bonding may be, for example, 80 to 160° C. The load in the thermocompression bonding may be, for example, 5 to 15 N. The heating time in the thermocompression bonding may be, for example, 0.5 to 20 seconds.

[0100] <Thermosetting process> In this step, the adhesive piece 10a of the semiconductor chip 60 with the adhesive piece bonded to the support member 80 is thermally cured. By (further) thermally curing the adhesive piece 10a or the cured adhesive piece 10ac bonding the semiconductor chip Wa to the support member 80, a stronger bond and fixation can be achieved. Furthermore, when the component (A) is silver particles (preferably silver particles produced by a reduction method), (further) thermally curing the adhesive piece 10a or the cured adhesive piece 10ac tends to make it easier to obtain a sintered body of the silver particles. When performing thermal curing, pressure may be applied simultaneously to achieve curing. 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. The temperature or pressure may be changed stepwise.

[0101] The adhesive piece 10a can be cured through a semiconductor chip bonding process or a thermal curing process to become a cured adhesive piece 10ac. When the component (A) is silver particles (preferably silver particles produced by a reduction method), the cured adhesive piece 10ac can contain a sintered body of silver particles. Therefore, the resulting semiconductor device can have excellent heat dissipation properties.

[0102] The method for manufacturing a semiconductor device may, if necessary, include a step of electrically connecting the tip of the terminal portion (inner lead) of the support member to an electrode pad on the semiconductor element with a bonding wire (wire bonding step). Examples of bonding wires that can be used include gold wire, aluminum wire, and copper wire. The temperature during wire bonding may be within a 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 by combining ultrasonic vibration energy and compression energy by applied pressure while the substrate is heated within the above temperature range.

[0103] The method for manufacturing a semiconductor device may optionally include a step of encapsulating the semiconductor element with an encapsulant (encapsulation step). This step is performed to protect the semiconductor element or bonding wires mounted on the support member. This step can be performed by molding the encapsulating resin (encapsulation resin) in a mold. The encapsulation resin may be, for example, an epoxy-based resin. The heat and pressure during encapsulation bury the support member and residue, preventing peeling due to air bubbles at the adhesive interface.

[0104] The method for manufacturing a semiconductor device may, if necessary, include a step (post-curing step) of completely curing the encapsulating resin that is insufficiently cured in the encapsulating step. Even if the adhesive piece is not thermally cured in the encapsulating step, in this step, the adhesive piece can be thermally cured together with the curing of the encapsulating resin, thereby enabling adhesive fixation. The heating temperature in this step can be appropriately set depending on the type of encapsulating resin, and may be, for example, in the range of 165 to 185°C, and the heating time may be approximately 0.5 to 8 hours.

[0105] The method for manufacturing a semiconductor device may, if necessary, include a step of heating the semiconductor element with adhesive 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, and then heated and melted using hot air or the like to perform soldering. Examples of heating methods include hot air reflow and infrared reflow. The heating method may be either a method of heating the entire device or a method of heating a localized area. The heating temperature may be, for example, within a range of 240 to 280°C.

[0106] [Semiconductor Devices] FIG. 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 200 shown in FIG. 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 film-like adhesive (cured adhesive piece 10ac). 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).

[0107] The semiconductor chip Wa (semiconductor element) may be, for example, an IC (integrated circuit), etc. Examples of the support member 80 include lead frames such as a 42 alloy lead frame and a copper lead frame; plastic films such as polyimide resin and epoxy resin; modified plastic films obtained by impregnating and curing a substrate such as a glass nonwoven fabric with a plastic such as polyimide resin or epoxy resin; and ceramics such as alumina.

[0108] The semiconductor device 200 has excellent heat dissipation properties because it includes the cured film adhesive as the adhesive member. [Example]

[0109] The present disclosure will be specifically described below based on examples, but the present disclosure is not limited to these examples.

[0110] (Examples 1 to 11 and Comparative Examples 1 to 7) <Preparation of adhesive varnish> A raw varnish was prepared by adding cyclohexanone as an organic solvent to components (A), (B), (C), and (D) according to the symbols and composition ratios (unit: parts by mass) shown in Tables 1 and 2. The raw varnish was stirred at 4,000 rpm for 20 minutes at a mixing temperature of 70°C using a Homo Disper (TKHOMO MIXER MARK II, manufactured by Tajima Chemical Machinery Co., Ltd.) to obtain an adhesive varnish. After the adhesive varnish was allowed to cool to 20-30°C, components (E) and (F) were added to the adhesive varnish, and the mixture was stirred overnight at 250 rpm using a Three-One Motor. In this way, adhesive varnishes were prepared in Examples 1 to 11 and Comparative Examples 1 to 7, each containing 61% by mass of components (A), (B), (C), and (D).

[0111] The symbols for each component in Tables 1 and 2 have the following meanings.

[0112] (A) Component: Metal particles (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 )):1.5μm) (A-2) Silver particles AG-5-1F (trade name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (laser 50% particle size (D 50 )):2.9μm) (A-3) Silver particles AG-2-1C (trade name, manufactured by DOWA Electronics Co., Ltd., shape: spherical, average particle size (laser 50% particle size (D 50 )):0.7μm)

[0113] (B) Component: Thermosetting resin (B-1) N-500P-10 (trade name, manufactured by DIC Corporation, cresol novolac epoxy resin, epoxy equivalent: 204 g / eq, softening point: 84°C) (B-2) EXA-830CRP (trade name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 159 g / eq, liquid at 25°C)

[0114] Component (C): Hardener (C-1) MEH-7800M (trade name, manufactured by Meiwa Chemical Co., Ltd., phenylaralkyl phenolic resin, hydroxyl group equivalent: 174 g / eq, softening point: 80°C) (C-2) PSM-4326 (trade name, manufactured by Gunei Chemical Industry Co., Ltd., phenol novolac type phenolic resin, hydroxyl group equivalent: 105 g / eq, softening point: 120°C)

[0115] (D) Component: Elastomer (D-1) SG-P3 (trade name, manufactured by Nagase ChemteX Corporation, acrylic rubber, weight average molecular weight: 800,000, Tg: -7°C)

[0116] Component (E): Coupling agent (E-1) A-1160 (trade name, manufactured by Nippon Unicar Co., Ltd., γ-ureidopropyltriethoxysilane)

[0117] (F) Component: Curing accelerator (F-1) 2PZ-CN (trade name, manufactured by Shikoku Chemicals Corporation, 1-cyanoethyl-2-phenylimidazole)

[0118] <Volume % calculation> The content (vol %) of component (A) is determined by multiplying the density of the film adhesive by x (g / cm 3 ), and the density of component (A) is y (g / cm 3 ), and the mass proportion of component (A) in the film adhesive was z (mass%), it was calculated using the following formula (I). The mass proportion of component (A) in the film adhesive was determined by thermogravimetric analysis using a thermogravimetric differential thermal analyzer (TG-DTA). The densities of the film adhesive and 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: 300mL / min Thermogravimetric differential thermal analyzer: Seiko Instruments Inc., TG / DTA220 Hydrometer: Alpha Mirage EW-300SG

[0119] <Preparation of film adhesive> Film-like adhesives were produced using the adhesive varnishes of Examples 1 to 11 and Comparative Examples 1 to 7. Each adhesive varnish was vacuum degassed, and then the adhesive varnish was applied to a support film, a polyethylene terephthalate (PET) film (thickness: 38 μm) that had been subjected to a release treatment. The applied adhesive varnish was heated and dried in two stages, first at 90°C for 5 minutes and then at 130°C for 5 minutes, to obtain film-like adhesives of Examples 1 to 11 and Comparative Examples 1 to 7 in a B-stage state and having a thickness of 25 μm on the support film.

[0120] <Measurement of shear viscosity, storage modulus, loss modulus, and tan δ of film adhesive at 110°C> The film adhesives (thickness: 25 μm) of Examples 1 to 11 and Comparative Examples 1 to 7 were each cut to a predetermined size to prepare 12 film pieces. The 12 film pieces were then laminated using a rubber roll on a hot plate at 70°C to prepare a laminate with a thickness of 300 μm. The laminate was then punched out with a φ9 mm punch to prepare samples. The shear viscosity, storage modulus, loss modulus, and tan δ of the prepared samples were measured at 110°C using a rotational viscoelasticity measuring device (manufactured by TA Instruments Japan, Inc., product name: ARES-RDA) under the following measurement conditions. During gap setting, the gap was adjusted so that the load on the sample was 10 to 15 g. The results are shown in Tables 1 and 2. (Measurement conditions) Disc plate: Aluminum, 8mm diameter Measurement frequency: 1Hz Heating rate: 5°C / min Strain: 5% Measurement temperature: 35~150℃ Initial load: 100g

[0121] <Evaluation of step filling ability> (Production of integrated dicing and die bonding film) A dicing tape having an adhesive layer was prepared, and the film-like adhesive (thickness: 25 μm) of Examples 1 to 11 and Comparative Examples 1 to 7 was attached to the adhesive layer of the dicing tape at 25°C, thereby obtaining integrated dicing and die bonding films of Examples 1 to 11 and Comparative Examples 1 to 7 having a die bonding film and dicing tape.

[0122] (Preparation of laminate) The dicing and die bonding integrated films of Examples 1 to 11 and Comparative Examples 1 to 7 were used. A film laminator (manufactured by Teikoku Taping System Co., Ltd.) was used to attach the adhesive layer (film-like adhesive) of the dicing and die bonding integrated film to a semiconductor wafer (thickness: 100 μm) to obtain a laminate.

[0123] (Preparation of evaluation samples) The semiconductor wafer in the resulting laminate was diced into individual pieces measuring 7.5 mm x 7.5 mm, and the individual semiconductor chips with adhesive strips were picked up using a die bonder (Besi, Esec2100sD PPP Plus). The pickup conditions were an expansion of 3 mm, a push-up load of 1 N, a pickup time of 100 ms, and a push-up speed of 10 mm / s. Next, a stepped substrate with a 4 μm step was prepared, and the semiconductor chips with adhesive strips were pressure-bonded to the stepped substrate via the adhesive strips under the following conditions: a stage temperature of 120°C for heating the substrate, a pressure bonding time of 1 second, and a pressure of 0.1 MPa. The stepped substrate with the bonded semiconductor chips was then heated at 110°C and a pressure of 0.5 MPa for 1 hour, and then at 170°C and a pressure of 0.5 MPa for 3 hours to thermally cure the adhesive strips, yielding a sample for evaluation.

[0124] (Evaluation of step filling ability of evaluation sample) The step-filling ability was evaluated by observing the gap between the uneven substrate and the heat-cured adhesive strip using an ultrasonic imaging device (Hitachi Construction Machinery FineTech Co., Ltd., FineSAT series FS2000II). A case in which no black shadows representing voids were observed between the uneven substrate and the heat-cured adhesive strip was rated "A," and a case in which black shadows representing voids were observed was rated "B." The results are shown in Tables 1 and 2.

[0125] <Measurement of thermal conductivity> (Preparation of film for measuring thermal conductivity) A laminated film having a thickness of 200 μm or more was prepared by laminating multiple sheets of each of the film-like adhesives of Examples 1 to 11 and Comparative Examples 1 to 7 using a rubber roll. The laminated film was then cut into a 1 cm × 1 cm piece, and the cut laminated film was thermally cured in a clean oven (manufactured by Espec Corporation) at 170°C for 3 hours to obtain a film for measuring thermal conductivity in a C-stage state.

[0126] (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: The results are shown in Tables 1 and 2. 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.

[0127] (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 equipment: Thermal diffusivity measurement equipment (manufactured by Netsch Japan Co., Ltd., product name: LFA447 nanoflash) Pulse width of pulsed light irradiation: 0.1ms Pulse light irradiation voltage: 236V Treatment of measurement sample: Both sides of the thermal conductivity measurement film are blackened with graphite spray. Measurement ambient temperature: 25°C ± 1°C

[0128] (Measurement of specific heat Cp (25℃)) 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 equipment: Differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., product name: Pyris1) Reference material: sapphire Heating rate: 10℃ / min Heating temperature range: Room temperature (25°C) to 60°C

[0129] (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. Measurement device: Electronic hydrometer (manufactured by Alpha Mirage Co., Ltd., product name: SD200L) ·Water temperature: 25℃

[0130] [Table 1]

[0131] [Table 2]

[0132] As shown in Tables 1 and 2, the parameters of shear viscosity and loss modulus of a film adhesive are highly correlated with the quality of its step-filling ability, and the film adhesives of Examples 1 to 11, which contain component (A) and satisfy either condition (i) or condition (ii) below, had good thermal conductivity and excellent step-filling ability compared to the film adhesives of Comparative Examples 1 to 7, which did not satisfy these conditions. On the other hand, it was found that parameters other than the shear viscosity and loss modulus of the film adhesive, such as storage modulus and tan δ (= loss modulus / storage modulus), have a low correlation with the quality of its step-filling ability.

[0133] Furthermore, the film-like adhesives of Examples 1 to 11, in which the content of component (A) was 70.0 mass% or more and the total content of components (B) and (C) was 13.0 mass% or more based on the total amount of components (A), (B), (C), and (D), had good thermal conductivity and excellent step-filling properties compared to the film-like adhesives of Comparative Examples 1 to 7, which did not satisfy these conditions.

[0134] From the above, it was confirmed that the film adhesive of the present disclosure is capable of producing a semiconductor device with excellent heat dissipation properties and has excellent step filling properties. [Industrial Applicability]

[0135] According to the present disclosure, a film-like adhesive that enables the manufacture of a semiconductor device with excellent heat dissipation properties and has excellent step-filling properties is provided. The present disclosure also provides an integrated dicing and die-bonding film using such a film-like adhesive. Furthermore, the present disclosure also provides a semiconductor device using such a film-like adhesive or dicing and die-bonding integrated film, and a method for manufacturing the same. [Explanation of symbols]

[0136] 10...adhesive layer, 10A...film-like adhesive, 10a...adhesive piece, 10ac...cured adhesive piece, 12...adhesive member, 20...support film, 30, 30a...pressure-sensitive adhesive layer, 40...base material layer, 50...dicing tape, 60...semiconductor chip with adhesive piece, 70...wire, 72...needle, 74...suction collet, 80...support member, 92...encapsulant layer, 94...solder ball, 100...dicing and die bonding integrated film, 200...semiconductor device, W...semiconductor wafer, Wa...semiconductor chip.

Claims

1. The composition contains metal particles, a thermosetting resin, a curing agent, and an elastomer, the content of the metal particles is 70.0 mass% or more based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer; The shear viscosity at 110°C is 30,000 Pa s or less, Film adhesive.

2. The loss modulus at 110°C is 200 kPa or less. The film adhesive according to claim 1 .

3. The composition contains metal particles, a thermosetting resin, a curing agent, and an elastomer, the content of the metal particles is 70.0 mass% or more based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer; The loss modulus at 110°C is 200 kPa or less. Film adhesive.

4. The composition contains metal particles, a thermosetting resin, a curing agent, and an elastomer, based on the total amount of the metal particles, the thermosetting resin, the curing agent, and the elastomer, The content of the metal particles is 70.0% by mass or more, The total content of the thermosetting resin and the curing agent is 13.0% by mass or more. Film adhesive.

5. The metal particles are conductive particles. The film-like adhesive according to any one of claims 1 to 4.

6. The metal particles are silver particles. The film-like adhesive according to any one of claims 1 to 4.

7. The adhesive sheet comprises, in this order, a base layer, a pressure-sensitive adhesive layer, and an adhesive layer made of the film-like adhesive according to any one of claims 1 to 6. Integrated dicing and die bonding film.

8. 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 A semiconductor device, wherein the adhesive member is a cured product of the film-like adhesive according to any one of claims 1 to 6.

9. a step of attaching a semiconductor wafer to the adhesive layer of the dicing and die bonding integrated film according to claim 7; dicing the semiconductor wafer to which the adhesive layer has been attached to produce a plurality of individual adhesive-attached semiconductor chips; a step of adhering the semiconductor chip with adhesive strip to a support member via the adhesive strip; A method for manufacturing a semiconductor device, comprising:

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