Manufacturing methods for semiconductor bonding films, die-cutting bonding integrated films, and semiconductor devices

Abstract

An adhesive film for semiconductors is disclosed. The adhesive film for semiconductors contains a thermosetting component, an elastomer, and an inorganic filler. The elastomer contains an acrylic resin having structural units derived from monomers having aromatic rings.

Description

Technical Field

[0001] This disclosure relates to a semiconductor adhesive film, a die-cutting bonding integrated film, and a method for manufacturing a semiconductor device. Prior Technology

[0002] Multi-chip packages (MCPs) are widely used to achieve high capacity by stacking multiple layers of semiconductor chips. Examples of stacked MCPs include wire-embedded and die-embedded semiconductor packages. The structure of a semiconductor package in which the wires are embedded in an adhesive film is sometimes called a film over wire (FOW). The structure of a semiconductor package in which the semiconductor die is embedded in an adhesive film is sometimes called a film over die (FOD). As an example of a semiconductor package using FOD, there is a semiconductor package having a controller chip disposed at the bottom layer and an adhesive film embedded therein (see Patent Document 1). In the manufacture of semiconductor packages with FOD or FOW structures, it is required that the semiconductor die or wires be sufficiently embedded in the adhesive film.

[0003] In recent years, with the increasing integration of wiring, the gaps between wires and spaces have become narrower, requiring adhesive films to have good HAST (Highly Accelerated Temperature and Humidity Stress Test) resistance. As a method to improve the HAST resistance of adhesive films, for example, a method using acrylic resin with a low proportion of acrylonitrile structural units has been proposed (see Patent Document 2).

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2014-175459 [Patent Document 2] International Publication No. 2020 / 067186

[0005] However, while conventional methods improve hash resistance, they sometimes reduce adhesion. Therefore, adhesive films are required to possess both hash resistance and adhesion. Summary of the Invention

[0006] Therefore, the main objective of this disclosure is to provide a semiconductor adhesive film with excellent HAST resistance and high adhesion.

[0007] Based on the research of the inventors, it was discovered that by using an acrylic resin having structural units derived from monomers having aromatic rings as an elastomer, it is possible to balance the HAST resistance and adhesion of the adhesive film for semiconductors, thereby completing the invention disclosed herein.

[0008] One aspect of this disclosure relates to an adhesive film for semiconductors. This adhesive film for semiconductors (hereinafter, sometimes simply referred to as "adhesive film") contains a thermosetting component, an elastomer, and an inorganic filler. The elastomer contains an acrylic resin having structural units derived from monomers having aromatic rings.

[0009] The adhesive film can have a thickness of 60 to 150 μm. In this case, the adhesive film can be a FOD adhesive film used to attach semiconductor wafers to a substrate while embedding other semiconductor wafers.

[0010] Another form of the adhesive film can have a thickness of 25 to 80 μm. In this case, the adhesive film can be an adhesive film for FOW (Field-of-Wave) applications, used to attach part or all of a wire embedded in and connected to other semiconductor wafers.

[0011] The elastomer may also contain acrylic resins that do not have structural units derived from monomers with aromatic rings. The weight-average molecular weight of the acrylic resins that do not have structural units derived from monomers with aromatic rings can be 500,000 or more.

[0012] Based on the total amount of adhesive film, the content of elastomer can be 10 to 60% by mass.

[0013] The content of inorganic filler can be 30 to 250 parts by mass relative to 100 parts by mass of thermosetting component.

[0014] Another aspect of this disclosure relates to a grain-cutting bonding integrated film. This grain-cutting bonding integrated film includes a cutting film and the aforementioned bonding film disposed on the cutting film.

[0015] Another aspect of this disclosure relates to a method for manufacturing a semiconductor device. One embodiment of the method for manufacturing a semiconductor device includes the step of attaching a second semiconductor wafer to a substrate on which a first semiconductor wafer is mounted, using the aforementioned adhesive film. In this case, the first semiconductor wafer is embedded in the adhesive film.

[0016] Another aspect of the manufacturing method for a semiconductor device includes the step of attaching a second semiconductor wafer to a first semiconductor wafer using the aforementioned adhesive film. In this case, a portion or all of the conductive wire is embedded in the adhesive film.

[0017] In one or another of the methods for manufacturing a semiconductor device, the first semiconductor wafer may be a controller wafer.

[0018] This disclosure includes [1] through

[12] . [1] A semiconductor adhesive film comprising a thermosetting component, an elastomer, and an inorganic filler. The aforementioned elastomer contains an acrylic resin having structural units derived from monomers having aromatic rings. [2] The semiconductor adhesive film as described in [1] has a thickness of 60 to 150 μm. [3] A semiconductor bonding film as described in [1] or [2], which is used to bond a semiconductor wafer to a substrate while embedding other semiconductor wafers. [4] The semiconductor adhesive film as described in [1] has a thickness of 25 to 80 μm. [5] A semiconductor bonding film as described in [1] or [4], used to bond a semiconductor wafer to the aforementioned other semiconductor wafer while embedding a portion or the entirety of a wire that connects to other semiconductor wafers. [6] A semiconductor adhesive film as described in any one of [1] to [5], wherein The aforementioned elastomer also contains acrylic resins that do not have structural units derived from monomers with aromatic rings. The aforementioned acrylic resins that do not have structural units derived from monomers with aromatic rings have a weight average molecular weight of 500,000 or more. [7] A semiconductor adhesive film as described in any one of [1] to [6], wherein Based on the total amount of the semiconductor adhesive film, the content of the aforementioned elastomer is 10 to 60% by mass. [8] A semiconductor adhesive film as described in any one of [1] to [7], wherein The content of the aforementioned inorganic filler is 30 to 250 parts by mass relative to 100 parts by mass of the aforementioned thermosetting component. [9] A grain-cutting and bonding integrated film, comprising: Cutting membrane; and The semiconductor adhesive film described in any one of [1] to [8] is disposed on the aforementioned cutting film.

[10] A method for manufacturing a semiconductor device, comprising the step of attaching a second semiconductor wafer to a substrate on which a first semiconductor wafer is mounted, using a semiconductor bonding film as described in [1] or [2]. The aforementioned first semiconductor wafer is embedded in the aforementioned adhesive film.

[11] A method for manufacturing a semiconductor device, comprising the step of attaching a second semiconductor wafer to a first semiconductor wafer using a semiconductor bonding film as described in [1] or [4]. The wire is connected to the aforementioned first semiconductor chip. Part or all of the aforementioned conductor is embedded in the aforementioned adhesive membrane.

[12] A method for manufacturing a semiconductor device as described in

[10] or

[11] , wherein The aforementioned first semiconductor chip is a controller chip. [Invention Effects]

[0019] According to this disclosure, a semiconductor bonding film with excellent HAST resistance and high adhesion is provided. Furthermore, according to this disclosure, a die-gluing integral film incorporating such a semiconductor bonding film is provided. Moreover, according to this disclosure, a method for manufacturing a semiconductor device using such semiconductor bonding films or die-gluing integral films is provided. Simple Explanation of the Diagram

[0020] Figure 1 is a schematic cross-sectional view showing one embodiment of the adhesive membrane. Figure 2 is a schematic cross-sectional view showing one embodiment of a laminate with an adhesive film. Figure 3 is a schematic cross-sectional view showing one embodiment of a laminate with an adhesive film. Figure 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device. Figure 5 is a step diagram illustrating one embodiment of a semiconductor device manufacturing method. Figure 6 is a step diagram illustrating one embodiment of a semiconductor device manufacturing method. Figure 7 is a step diagram illustrating one embodiment of a semiconductor device manufacturing method. Figure 8 is a step diagram illustrating one embodiment of a semiconductor device manufacturing method. Figure 9 is a step diagram illustrating one embodiment of a semiconductor device manufacturing method. Figure 10 is a schematic cross-sectional view showing another embodiment of the semiconductor device. Figure 11 is a schematic cross-sectional view showing another embodiment of the semiconductor device. Implementation

[0021] This disclosure is not limited to the following examples. In the following examples, unless otherwise explicitly stated, the constituent elements (including steps, etc.) are not essential. The sizes of the constituent elements in each figure are conceptual sizes, and the relative sizes between the constituent elements are not limited to the relationships shown in the figures. The numerical values ​​and their ranges illustrated below also do not limit this disclosure.

[0022] In this specification, the numerical range represented by "~" indicates the range encompassed by the values ​​before and after "~" as the minimum and maximum values, respectively. Within the numerical ranges described in this specification, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of other numerical ranges described in different stages. Furthermore, the upper or lower limit of the numerical range described in this specification can also be replaced by the values ​​shown in the embodiments.

[0023] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar terms such as (meth)acrylate, (meth)acrylic acid, (meth)acrylic acid copolymer, etc.

[0024] Unless otherwise specified, the materials listed below may be used alone or in combination of two or more. In the case of a composition containing multiple substances that conform to the components, unless otherwise specified, the content of each component in the composition refers to the total amount of those multiple substances present in the composition.

[0025] [Semiconductor adhesive film (adhesive film)] Figure 1 is a schematic cross-sectional view showing one embodiment of the adhesive film. The adhesive film 10 shown in Figure 1 contains a thermosetting component (hereinafter, sometimes referred to as "component (A)"), an elastomer (hereinafter, sometimes referred to as "component (B)"), and an inorganic filler (hereinafter, sometimes referred to as "component (C)"). In addition to components (A), (B), and (C), the adhesive film 10 may also contain a curing accelerator (hereinafter, sometimes referred to as "component (D)"), a coupling agent (hereinafter, sometimes referred to as "component (E)"), and other components. The adhesive film 10 can be a film formed from a thermosetting adhesive containing components (A), (B), and (C). The adhesive film 10 can be in a semi-cured (stage B) state. After curing treatment, the adhesive film 10 can become a cured (stage C) state.

[0026] (A) Composition: Thermosetting components (A) The component may contain (A1) a thermosetting resin, which is a compound having functional groups that form a cross-linked structure through a thermosetting reaction, and may further contain (A2) a curing agent that reacts with the thermosetting resin. From the viewpoint of adhesion, the thermosetting resin may contain an epoxy resin, which is a compound having epoxy groups. In this case, the curing agent may contain a phenolic resin, which is a compound having phenolic hydroxyl groups.

[0027] Examples of epoxy resins used as thermosetting resins include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; phenolic varnish type epoxy resin; cresol varnish type epoxy resin; bisphenol A varnish type epoxy resin; bisphenol F varnish type epoxy resin; pyridine type epoxy resin; triphenyl alkyl-containing epoxy resin; pyridine alkyl-containing epoxy resin; pyridine methane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; biphenyl aralkyl type epoxy resin; naphthalene type epoxy resin; polyfunctional phenols; anthracene and other polycyclic aromatic diglycidyl ether compounds, etc. These can be used alone or in combination of two or more. In terms of the film's viscosity, flexibility, etc., epoxy resins may also contain cresol varnish-type epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins, or combinations thereof.

[0028] Epoxy resins can contain liquid epoxy resins that are liquid at 30°C (epoxy resins with a softening point below 40°C). That is, epoxy resins can be a combination of liquid epoxy resins and solid epoxy resins that are solid at 30°C (epoxy resins with a softening point above 40°C). Furthermore, in this specification, the softening point refers to the value measured according to JIS K7234 using the ring and ball method. Based on the total amount of adhesive film, the content of liquid epoxy resin can be 3-15% by mass. The presence of liquid epoxy resin in thermosetting resins tends to improve the flexibility of the adhesive film. Furthermore, the combination of liquid and solid epoxy resins tends to improve the embedding capability of semiconductor wafers and wires.

[0029] Commercially available liquid epoxy resins include, for example, EXA-830CRP (trade name, manufactured by DIC Corporation, liquid at 30°C), YDF-8170C (trade name, manufactured by NIPPON STEEL Chemical & Material Co., Ltd., liquid at 30°C), and EP-4088S (trade name, manufactured by ADEKA CORPORATION, liquid at 30°C).

[0030] There is no particular limitation on the epoxy equivalent of epoxy resin, which can be 90~300 g / eq or 110~290 g / eq. When the epoxy equivalent of epoxy resin is within such a range, it tends to maintain the volume strength of the adhesive film and easily ensure the flowability of the thermosetting adhesive during film formation.

[0031] Examples of phenolic resins used as curing agents include phenolic varnish-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 dihydroxynaphthol with aldehyde compounds such as formaldehyde under an acidic catalyst; phenolic aralkyl resins and naphthol aralkyl resins synthesized from allylated bisphenol A, allylated bisphenol F, allylated naphthalene glycol, phenolic varnish, phenol, and / or naphthols with dimethoxy-p-xylene or bis(methoxymethyl)biphenyl. These can be used alone or in combination of two or more. Phenolic resins may contain phenylaralkyl type phenolic resins, phenolic varnish resins, or combinations thereof.

[0032] The hydroxyl equivalent of phenolic resin can be 70 g / eq or higher, or 70-300 g / eq. When the hydroxyl equivalent of phenolic resin is 70 g / eq or higher, the storage elastic modulus of the adhesive film tends to increase further. When the hydroxyl equivalent of phenolic resin is 300 g / eq or lower, foaming and degassing can be further suppressed.

[0033] Commercially available phenolic resins include, for example, PSM-4326 (trade name, manufactured by Gunei Chemical Industry Co., Ltd., softening point: 120℃), J-DPP-140 (trade name, manufactured by JFE Chemical Corporation, softening point: 140℃), GPH-103 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 99~106℃), MEH-7800M (trade name, manufactured by MEIWA PLASTIC INDUSTRIES, LTD., softening point: 80℃), J-DPP-85 (trade name, manufactured by JFE Chemical Corporation, softening point: 85℃), and MEH-5100-5S (trade name, manufactured by MEIWA PLASTIC INDUSTRIES, LTD., softening point: 65℃).

[0034] When a thermosetting resin contains epoxy resin and a curing agent contains phenolic resin, from the viewpoint of curability, the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenolic resin (epoxy equivalent: hydroxyl equivalent) can be 0.30 / 0.70~0.70 / 0.30, 0.35 / 0.65~0.65 / 0.35, 0.40 / 0.60~0.60 / 0.40, or 0.45 / 0.55~0.55 / 0.45. When this equivalent ratio is 0.30 / 0.70 or higher, there is a tendency to obtain more sufficient curability. When this 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 flowability.

[0035] The softening point of the curing agent can be 50~200℃ or 60~150℃. Curing agents with a softening point below 200℃ tend to have good compatibility with thermosetting resins.

[0036] Based on the total amount of adhesive film, the content of component (A) (the total content of thermosetting resin and curing agent) can be 10% by mass or more, or 15% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, or 30% by mass or more. When the content of component (A) is 10% by mass or more based on the total amount of adhesive film, there is a tendency to improve the adhesion of the adhesive film. From the viewpoint of film formability, based on the total amount of adhesive film, the content of component (A) can be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 45% by mass or less.

[0037] (B) Component: Elastomer (B) The component may contain an acrylic resin having structural units derived from monomers having aromatic rings (hereinafter, sometimes referred to as "first acrylic resin"), and further contain an acrylic resin not having structural units derived from monomers having aromatic rings (hereinafter, sometimes referred to as "second acrylic resin").

[0038] The first acrylic resin is an acrylic resin (acrylic rubber) having structural units derived from monomers having a (meth)acrylic group as its main component. Examples of monomers having a (meth)acrylic group include (meth)acrylate, (meth)acrylic acid, and (meth)acrylonitrile. Based on the total amount of structural units constituting the first acrylic resin, the content of structural units derived from monomers having a (meth)acrylic group can be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The first acrylic resin may have structural units derived from (meth)acrylate with crosslinking functional groups such as epoxy, alcoholic or phenolic hydroxyl, or carboxyl groups. When the first acrylic resin has structural units derived from (meth)acrylate with crosslinking functional groups, the adhesion strength after curing can be improved by reacting with component (A) through heating.

[0039] The first acrylic resin has structural units derived from monomers having aromatic rings. By including such a first acrylic resin in component (B), there is a tendency to improve the adhesion of the adhesive film. Examples of monomers having aromatic rings include monomers having both an aromatic ring and a (meth)acrylic group (monomers having both an aromatic ring and a (meth)acrylic group), and monomers having an aromatic ring but not a (meth)acrylic group (monomers having both an aromatic ring and not a (meth)acrylic group).

[0040] Examples of monomers having an aromatic ring and a (meth)acrylic group include phenyl (meth)acrylate, benzyl (meth)acrylate, hydroxybenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, hydroxyphenyl (meth)acrylate, methacrylic oxyethyl phthalate, phenoxy polyethylene glycol (meth)acrylate, and ethoxylated nonylphenyl ether (meth)acrylate.

[0041] Examples of monomers having an aromatic ring but not a (meth)acrylic acid group include styrene; styrene derivatives such as α-methylstyrene, ethylstyrene, butylstyrene, isobutylstyrene, propylstyrene, isopropylstyrene, fluorostyrene, chlorostyrene, bromostyrene, styrene sulfonic acid, and hydroxystyrene (vinylphenol); aromatic vinyl compounds and their derivatives such as vinyltoluene, vinylpyridine, isopropenylphenol, allylphenol, vinylnaphthalene, vinylanthracene, vinylphenanthrene, and vinylpyrene.

[0042] Based on the total amount of structural units constituting the first acrylic resin, the content of structural units derived from monomers having aromatic rings can be 1% or more by mass, 3% or more by mass, or 5% or more by mass, and can be less than 30% by mass, less than 25% by mass, or less than 20% by mass.

[0043] The glass transition temperature (Tg) of the first acrylic resin can be above 0°C or above 3°C. When the Tg of the first acrylic resin is above 0°C, the adhesion strength of the adhesive film can be further improved, thus preventing the adhesive film from becoming too flexible. This makes it easier to cut the adhesive film during wafer dicing, preventing burrs. There is no particular upper limit to the Tg of the first acrylic resin; for example, it can be below 55°C, below 50°C, below 45°C, below 40°C, below 35°C, below 30°C, or below 25°C. When the Tg of the first acrylic resin is below 55°C, it tends to improve the lamination properties of the wafer. This improves the adhesion force and enhances the prevention of wafer scattering after dicing. Furthermore, it prevents chipping during dicing due to reduced adhesion to the semiconductor wafer. In this specification, the glass transition temperature (Tg) refers to a value measured using a DSC (Differential Scanning Calorimeter) (e.g., Rigaku Corporation's Thermo Plus 2). By adjusting the types and contents of the structural units that make up the first acrylic resin, the Tg of the first acrylic resin can be adjusted to the desired range.

[0044] The weight-average molecular weight (Mw) of the first acrylic resin can be 100,000 or more, 200,000 or more, or 300,000 or more, and can be less than 3 million, less than 2 million, or less than 1 million. When the Mw of the first acrylic resin is within such a range, film formation properties, film strength, flexibility, tackiness, etc., can be appropriately controlled, and reflow properties are excellent, which can improve embedding performance. In addition, in this specification, Mw refers to the value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene. Furthermore, when multiple peaks are observed in GPC, the weight-average molecular weight of the peak with the highest peak intensity is defined as the weight-average molecular weight in this specification.

[0045] Based on the total amount of component (B), the content of the first acrylic resin can be 20-100% by mass. When the content of the first acrylic resin is 20% by mass or more based on the total amount of component (B), it tends to easily balance the hardness resistance and adhesion of the adhesive film. Based on the total amount of component (B), the content of the first acrylic resin can be 22% by mass or more or 25% by mass or more, and can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less.

[0046] The second acrylic resin is an acrylic resin (acrylic rubber) having structural units derived from monomers with (meth)acrylic groups as its main component and lacking structural units derived from monomers with aromatic rings. That is, the second acrylic resin can be described as an acrylic resin (acrylic rubber) obtained by removing structural units derived from monomers with aromatic rings from the first acrylic resin. Based on the total amount of structural units constituting the second acrylic resin, the content of structural units derived from monomers with (meth)acrylic groups can be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The second acrylic resin may have structural units derived from (meth)acrylates with crosslinking functional groups such as epoxy groups, alcoholic or phenolic hydroxyl groups, and carboxyl groups. When the second acrylic resin has structural units derived from (meth)acrylates with crosslinking functional groups, the adhesion strength after curing can be improved by reacting with component (A) through heating.

[0047] The glass transition temperature (Tg) of the second acrylic resin can be above 5°C or above 8°C. There is no particular upper limit to the Tg of the second acrylic resin, for example, it can be below 55°C, below 50°C, below 45°C, below 40°C, below 35°C, below 30°C, or below 25°C.

[0048] The weight average molecular weight (Mw) of the second acrylic resin can be above 500,000, above 600,000, or above 700,000, and can be below 3 million, below 2 million, or below 1 million.

[0049] Based on the total amount of component (B), the content of the second acrylic resin can be 0 to 80% by mass. Based on the total amount of component (B), the content of the second acrylic resin can be less than 78% by mass or less than 75% by mass, and can be more than 10% by mass, more than 20% by mass, more than 30% by mass, more than 40% by mass, more than 50% by mass, more than 55% by mass, or more than 60% by mass.

[0050] From the viewpoint of HAST resistance, the first acrylic resin and the second acrylic resin can be acrylic resins with a low proportion of structural units derived from (meth)acrylonitrile. For example, the first acrylic resin and the second acrylic resin can be acrylic resins that satisfy the following formula (1) when the area of ​​the absorption peak from the stretching vibration of the carbonyl group is set as PA CO and the area of ​​the peak from the stretching vibration of the nitrile group is set as PA CN in the infrared absorption spectrum (IR spectrum). PA CN / PA CO≤0.100 (1)

[0051] Here, the carbonyl group mainly comes from (meth)acrylate, which is a structural unit, and the nitrile group mainly comes from (meth)acrylonitrile, which is a structural unit. Furthermore, the area of ​​the absorption peak from the stretching vibration of the carbonyl group (PACO) and the area of ​​the peak from the stretching vibration of the nitrile group (PACN) can be calculated, for example, by the following method.

[0052] First, the transmission IR spectrum of a mixture of first and second acrylic resins, or an adhesive film containing them, is measured using the KBr ingot method, with absorbance on the vertical axis and wavenumber (cm⁻¹) on the horizontal axis. For example, an FT-IR6300 (manufactured by JASCO Corporation, light source: high-brightness ceramic light source, detector: DLATGS) can be used for IR spectroscopy measurements. In the displayed spectrum, the area of ​​the absorption peak from the stretching vibration of the carbonyl group (PACO) is defined as the area of ​​absorbance enclosed by the straight line connecting the two points of 1650 cm⁻¹ and 1800 cm⁻¹ on the spectrum, with the spectrum and the baseline as the baseline. The area of ​​the peak from the stretching vibration of the nitrile group (PACN) is defined as the area of ​​absorbance enclosed by the straight line connecting the two points of 2230 cm⁻¹ and 2300 cm⁻¹ on the spectrum, with the spectrum and the baseline as the baseline. Based on these definitions of PACO and PACN, PACN / PACO can be calculated.

[0053] The PA CN / PA CO ratio of the first and second acrylic resins can be 0.100 or less, or 0.090 or less, 0.080 or less, 0.070 or less, 0.060 or less, 0.050 or less, 0.040 or less, 0.030 or less, or 0.020 or less. When the PA CN / PA CO ratio is 0.100 or less, the cohesive strength of the acrylic resin decreases, thus tending to increase embedding properties.

[0054] In addition to the first acrylic resin and the second acrylic resin, component (B) may also contain other elastomers. Examples of other elastomers include, for example, polyester resin, polyamide resin, polyimide resin, silicone resin, butadiene resin, and modified forms of these resins. Based on the total amount of component (B), the content of other elastomers may be 0 to 20% by mass.

[0055] Based on the total amount of adhesive film, the content of component (B) can be 10-60% by mass. When the content of component (B) is 10% by mass or more based on the total amount of adhesive film, there is a tendency to improve the embedding properties of the adhesive film; when it is 60% by mass or less, there is a tendency to improve the adhesion of the adhesive film. Based on the total amount of adhesive film, the content of component (B) can be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and can be 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 38% by mass or less.

[0056] (C) Composition: Inorganic filler (C) Component may be, for example, at least one selected from aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, and silicon dioxide. From the viewpoint of adjusting melt viscosity, (C) component may contain silicon dioxide.

[0057] From a flowability perspective, the average particle size of component (C) can be 0.01 μm (10 nm) or more, 0.03 μm (30 nm) or more, 0.05 μm (50 nm) or more, or 0.1 μm (100 nm) or more, and can be 1.5 μm (1500 nm) or less, 1.0 μm (1000 nm) or less, 0.8 μm (800 nm) or less, or 0.6 μm (600 nm) or less. Two or more components (C) with different average particle sizes can also be combined. Here, the average particle size refers to the particle size at the 50% cumulative frequency in the particle size distribution determined by laser diffraction / scattering. Furthermore, the average particle size of component (C) can also be determined by using an adhesive film containing component (C). In this case, the residue obtained by decomposing the resin components by heating the adhesive film is dispersed in a solvent to prepare a dispersion. Based on the particle size distribution obtained by applying laser diffraction / scattering method to it, the average particle size of component (C) can be determined.

[0058] The adhesive membrane may contain a first inorganic filler and a second inorganic filler that meet the following conditions. By containing the first inorganic filler and the second inorganic filler, the embeddability of the adhesive membrane can be improved, thereby improving the tensile strength and adhesion after curing. • The average particle size of the first inorganic filler is 300~1000nm. • The average particle size of the second inorganic filler is 0.05 to 0.70 times that of the first inorganic filler. Based on the total amount of adhesive film, the total content of the first inorganic filler and the second inorganic filler ((C) component) is 10~60% by mass.

[0059] The average particle size of the first inorganic filler is 300~1000nm, which can be above 350nm, above 400nm, or above 450nm, and can be below 900nm, below 800nm, below 700nm, or below 600nm.

[0060] The average particle size of the second inorganic filler can be less than 300 nm, or it can be less than 250 nm, less than 220 nm, or less than 200 nm. For example, the average particle size of the second inorganic filler can be greater than 10 nm, greater than 50 nm, or greater than 100 nm.

[0061] These average particle sizes refer to the particle sizes at the cumulative frequency of 50% in the particle size distribution determined by laser diffraction / scattering. Furthermore, the average particle sizes of the first and second inorganic fillers can also be determined using an adhesive film containing the first and second inorganic fillers. In this case, the residue obtained by decomposing the resin components through heating the adhesive film is dispersed in a solvent to prepare a dispersion. Based on the particle size distribution obtained by applying laser diffraction / scattering, the values ​​of peaks in the range of 300–1000 nm can be used as the average particle size of the first inorganic filler, and the values ​​of peaks in the range less than 300 nm can be used as the average particle size of the second inorganic filler.

[0062] The average particle size of the second inorganic filler is 0.05 to 0.70 times the average particle size of the first inorganic filler. The average particle size of the second inorganic filler can be more than 0.10, more than 0.20, or more than 0.30 times the average particle size of the first inorganic filler, and can be less than 0.60, less than 0.50, or less than 0.40 times the average particle size of the first inorganic filler.

[0063] Based on the total amount of the adhesive film, the content of the first inorganic filler can be 5 to 60% by mass, or it can be more than 6%, more than 8%, or more than 10% by mass, and it can be less than 55% by mass, less than 45% by mass, less than 40% by mass, less than 35% by mass, or less than 30% by mass.

[0064] Based on the total amount of the adhesive film, the content of the second inorganic filler can be 0 to 40% by mass, or it can be 3% or more by mass, 5% or more by mass, 10% or more by mass, 12% or more by mass, or 15% or more by mass, and it can be less than 35% by mass, less than 30% by mass, or less than 25% by mass.

[0065] Based on the total amount of the adhesive film, the total content ((C) component) of the first inorganic filler and the second inorganic filler is 10 to 60% by mass, which can be more than 15% by mass, more than 18% by mass, more than 20% by mass, more than 25% by mass, or more than 30% by mass, and can be less than 55% by mass, less than 52% by mass, or less than 50% by mass.

[0066] The mass percentage of the first inorganic packing relative to the total of the first and second inorganic packings ((C) composition) can be 40 to 100% by mass, or 45% or more, 50% or more, or 55% or more by mass, and can be less than 95% by mass, less than 90% by mass, or less than 85% by mass.

[0067] The mass percentage of the second inorganic packing relative to the total of the first and second inorganic packings ((C) composition) can be 0 to 60% by mass, or more than 5%, more than 10%, or more than 15% by mass, and can be less than 55%, less than 50%, or less than 45% by mass.

[0068] The content of component (C) can be 30 to 250 parts by weight relative to 100 parts by weight of component (A) (total of thermosetting resin and curing agent). When the content of component (C) is within this range, there is a tendency to improve the adhesion of the adhesive film. The content of component (C) can be 35 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, or 55 parts by weight or more, and can be 220 parts by weight or less, 200 parts by weight or less, 180 parts by weight or less, 160 parts by weight or less, 150 parts by weight or less, 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, or 100 parts by weight or less.

[0069] (D) Ingredients: Curing accelerator Examples of components (D) include imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These can be used alone or in combination of two or more. From a reactivity point of view, component (D) can also be imidazoles and their derivatives.

[0070] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. These can be used alone or in combination of two or more.

[0071] (E) Component: Coupling agent (E) Components may also be silane coupling agents. Examples of silane coupling agents include γ-ureopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane. These may be used alone or in combination of two or more.

[0072] The membrane may also contain other components. Examples of other components include pigments, ion scavengers, and antioxidants.

[0073] Based on the total amount of the adhesive film, the total content of component (D), component (E) and other components can be more than 0.1% by mass, more than 0.3% by mass, or more than 0.5% by mass, or less than 30% by mass, less than 20% by mass, less than 10% by mass, or less than 5% by mass.

[0074] The adhesive film 10 can be formed, for example, by coating a thermosetting adhesive onto a support film. In the formation of the adhesive film 10, a varnish of a thermosetting adhesive (adhesive varnish) can also be used. When using an adhesive varnish, the adhesive varnish is prepared by mixing or kneading components (A), (B), and (C), and any other components added as needed, in a solvent. The obtained adhesive varnish is then coated onto the support film, heated, and dried to remove the solvent, thereby obtaining the adhesive film 10.

[0075] The supporting film is not particularly limited as long as it can withstand the aforementioned heating and drying. Examples include polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyethylene naphthalate film, and polymethylpentene film. The supporting film can be a multilayer film composed of two or more materials, or it can be a substrate whose surface is treated with silicone-based, silicon dioxide-based, or other release agents. The thickness of the supporting film can be, for example, 10–200 μm or 20–170 μm.

[0076] Mixing or kneading can be carried out using common dispersers such as mixers, pounders, three-roll mills, and ball mills, and these can be combined appropriately.

[0077] There are no restrictions on the solvent used to prepare adhesive varnishes, as long as it can uniformly dissolve, mix, or disperse the components; conventionally known solvents can be used. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, as well as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, and xylene. From the viewpoint of drying speed and price, methyl ethyl ketone or cyclohexanone can be used as the solvent.

[0078] As a method for applying adhesive varnish to a support film, known methods can be used, such as blade coating, roller coating, spraying, gravure coating, bar coating, and curtain coating. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently evaporated; for example, it can be 50-150°C for 1-30 minutes.

[0079] The thickness of the adhesive film 10 can be, for example, 1 μm or more, 3 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, or 80 μm or more, and can be less than 200 μm, 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, or 60 μm or less. When the adhesive film 10 is for FOD (For-The-World) applications, in order to properly embed it into the entire semiconductor wafer (e.g., a controller wafer), the thickness of the adhesive film 10 can be, for example, 40-200 μm, 60-150 μm, or 80-120 μm. When the adhesive film 10 is for FOW (For-The-World) applications, in order to embed wires so that the wires do not contact the semiconductor wafer, the thickness of the adhesive film 10 can be, for example, 20-120 μm, 25-80 μm, or 30-60 μm.

[0080] From the viewpoint of preventing damage or contamination, the adhesive film 10 fabricated on the support film may also have a cover film on the side of the adhesive film opposite to the support film. Examples of cover films include polyethylene film, polypropylene film, and surface release agent treated film. The thickness of the cover film may be, for example, 15~200μm or 30~170μm.

[0081] Then the film 10 can be used, for example, as a protective sheet to protect the back side of the semiconductor element (semiconductor wafer) of the flip-chip semiconductor device, or as a sealing sheet to seal the surface of the semiconductor element (semiconductor wafer) of the flip-chip semiconductor device and the adherend.

[0082] [Integrated membrane with grain cutting and bonding] Figures 2 and 3 are schematic cross-sectional views showing one embodiment of the laminate with an adhesive film. The adhesive film 10 can also be supplied in the form of the laminate shown in Figure 2 or Figure 3. The laminate 100 shown in Figure 2 includes a substrate layer 20 and an adhesive film 10 disposed on the substrate layer 20. The laminate 110 shown in Figure 3 also includes a protective film 30, which is disposed on the side of the adhesive film 10 opposite to the substrate layer 20 relative to the laminate 100.

[0083] The substrate layer 20 can be the same resin film as the support film. The thickness of the substrate layer 20 can be, for example, 10~200μm or 20~170μm.

[0084] The substrate layer 20 can also be a dicing film. A laminate of the substrate layer 20 as a dicing film can be used as a dicing grain bonding integrated film. The dicing grain bonding integrated film can be in the form of a film, sheet, or strip.

[0085] Examples of dicing films include polytetrafluoroethylene (PTFE) films, polyethylene terephthalate (PET) films, polyethylene films, polypropylene films, polymethylpentene (PMM) films, and polyimide films. Depending on the requirements, the dicing film can also be a resin film that has undergone surface treatment through primer coating, UV treatment, corona discharge treatment, polishing, or etching. The dicing film can be adhesive. An adhesive dicing film can be, for example, an adhesive resin film, or a laminated film having a resin film and an adhesive layer disposed on one side thereof. The adhesive layer can be formed from a non-UV-curable or UV-curable adhesive. A non-UV-curable adhesive is one that exhibits constant adhesion under short-term pressure. A UV-curable adhesive is one whose adhesion decreases upon exposure to ultraviolet light. The thickness of the adhesive layer can be appropriately set according to the shape and size of the semiconductor device, for example, it can be 1~100 μm, 5~70 μm, or 10~40 μm. From the perspective of economy and membrane operability, the thickness of the substrate layer 20 of the cutting membrane can be 60~150μm or 70~130μm.

[0086] The protective film 30 can be the same resin film as the cover film. The thickness of the protective film 30 can be, for example, 15~200μm or 30~170μm.

[0087] Semiconductor devices and manufacturing methods thereof Figure 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device, illustrating an example of a semiconductor device manufactured using an adhesive film. The semiconductor device 200 shown in Figure 4 mainly comprises a substrate 14, a first semiconductor wafer Wa and a second semiconductor wafer Waa mounted on the substrate 14, a sealing layer 42 sealing the second semiconductor wafer Waa, and an adhesive film 10 bonding the second semiconductor wafer Waa to the substrate 14. The substrate 14 has an organic substrate 90 and circuit patterns 84 and 94 disposed on the organic substrate 90. The first semiconductor wafer Waa is bonded to the substrate 14 by an adhesive 41. A first conductive line 88 is connected to the first semiconductor wafer Waa, and the first semiconductor wafer Waa is electrically connected to the circuit pattern 84 via the first conductive line 88. The entire first semiconductor wafer Waa and the entire first conductive line 88 are embedded in the adhesive film 10. A second conductive line 98 is connected to the second semiconductor wafer Waa, and the second semiconductor wafer Waa is electrically connected to the circuit pattern 84 via the second conductive line 98. The entire second semiconductor wafer Waa and the entire second conductive line 98 are embedded in the sealing layer 42.

[0088] Figures 5, 6, 7, 8, and 9 are step diagrams illustrating one embodiment of a method for manufacturing a semiconductor device, specifically an example of the method for manufacturing the semiconductor device 200 shown in Figure 4. The method shown in Figures 5-9 includes the following steps: attaching a first semiconductor wafer Wa to a substrate 14 via an adhesive 41; providing a first conductive line 88 connecting the first semiconductor wafer Wa to the substrate 14 (circuit pattern 84); preparing a wafer with an adhesive layer, having a second semiconductor wafer Wbb and an adhesive film 10 attached thereto; pressing the adhesive-bearing wafer onto the substrate 14, thereby attaching the second semiconductor wafer Waa to the substrate 14 such that the first semiconductor wafer Wa and the first conductive line 88 are embedded in the adhesive film 10; and providing a second conductive line 98 connecting the second semiconductor wafer Waa to the substrate 14 (circuit pattern 84). Afterward, by forming a sealing layer 44, the semiconductor device 200 shown in Figure 4 can be obtained.

[0089] The thickness of the first semiconductor wafer Wa can be 10~170μm. The first semiconductor wafer Wa can be a controller wafer used to drive the semiconductor device 200. The first semiconductor wafer Wa can be a flip-chip type wafer. The size of the first semiconductor wafer Wa is typically smaller than or equal to the size of the second semiconductor wafer Waa. The adhesive 41 between the first semiconductor wafer Wa and the substrate 14 can be a known semiconductor adhesive used in the art.

[0090] As shown in Figure 5, the substrate 14 (circuit pattern 84) and the first semiconductor wafer Wa are electrically connected via a first wire 88. The first wire 88 connecting the first semiconductor wafer Wa and the substrate 14 (circuit pattern 84) can be, for example, a gold wire, an aluminum wire, or a copper wire. The heating temperature used to connect the first wire 88 can be in the range of 80~250°C or 80~220°C. The heating time used to connect the first wire 88 can be from a few seconds to a few minutes. To connect the first wire 88, vibrational energy generated by ultrasound and pressure energy generated by applying pressure can also be applied.

[0091] The adhesive-coated wafer formed from the second semiconductor wafer Waa and the adhesive film 10 can be prepared, for example, using a die-bonding integrated film having the same structure as the stack 100 shown in FIG. 2. In this case, for example, the stack 100 (die-bonding integrated film) is attached to one side of the semiconductor wafer with the adhesive film 10 in contact with the semiconductor wafer. The side on which the adhesive film 10 is attached can be the circuit side of the semiconductor wafer or the back side opposite to it. The semiconductor wafer on which the stack 100 (die-bonding integrated film) is attached is divided by dicing, thereby forming a monolithic second semiconductor wafer Waa. Examples of dicing include cutting with a rotary blade, creating modified regions on the semiconductor wafer by laser, and stealth dicing to expand the substrate layer. The second semiconductor wafer Waa and the divided adhesive film 10 are picked up together. When the adhesive layer of the cutting film is formed by an ultraviolet-curable adhesive, the adhesive strength of the adhesive layer can be reduced by irradiating the adhesive layer with ultraviolet light before picking up the second semiconductor wafer Waa, as needed.

[0092] The second semiconductor wafer Waa can have a width of less than 20 mm. The width (or the length of one side) of the second semiconductor wafer Waa can be 3~15 mm or 5~10 mm.

[0093] The semiconductor wafer used to form the second semiconductor chip Waa can be, for example, a thin semiconductor wafer with a thickness of 10 to 100 μm. Besides monocrystalline silicon, the semiconductor wafer can also be polycrystalline silicon, various ceramics, gallium arsenide, and other compound semiconductor wafers. The second semiconductor chip Waa can also be formed from the same semiconductor wafer.

[0094] As shown in Figure 7, a wafer with adhesive formed from the adhesive film 10 and the second semiconductor wafer Waa is placed such that the first conductive line 88 and the first semiconductor wafer Waa are covered by the adhesive film 10. Next, as shown in Figure 8, the second semiconductor wafer Waa is fixed to the substrate 14 by pressing it onto the substrate 14. The heating temperature used for pressing can be 50~200℃ or 100~150℃. If the heating temperature used for pressing is high, the adhesive film 10 softens, thus tending to improve embeddability. The pressing time can be 0.5~20 seconds or 1~5 seconds. The pressing pressure can be 0.01~5MPa or 0.02~2MPa.

[0095] Alternatively, after pressing, the structure containing the adhesive film 10 can be further heated to cure the adhesive film 10. The curing temperature and time can be appropriately set according to the curing temperature of the adhesive film 10. The temperature can also be varied in stages. The heating temperature can be, for example, 40~300℃ or 60~200℃. The heating time can be, for example, 30~300 minutes.

[0096] As shown in Figure 9, the substrate 14 and the second semiconductor wafer Waa are electrically connected via a second wire 98. The type and connection method of the second wire 98 can be the same as those of the first wire 88.

[0097] Subsequently, a sealing layer 42 is formed from a sealing material to form a sealing circuit pattern 84, a second conductive wire 98, and a second semiconductor wafer Waa. The sealing layer 42 can be formed, for example, by a conventional method using a mold. After the sealing layer 42 is formed, the adhesive film 10 and the sealing layer 42 can be further thermally cured by heating. For example, the heating temperature can be 165~185°C, and the heating time can be approximately 0.5~8 hours.

[0098] Figure 10 is a schematic cross-sectional view showing another embodiment of the semiconductor device. The semiconductor device 201 mainly comprises a substrate 14, a first semiconductor wafer Wa and a second semiconductor wafer Waa mounted on the substrate 14, a sealing layer 42 sealing the first semiconductor wafer Waa and the second semiconductor wafer Waa, and an adhesive film 10 attaching the second semiconductor wafer Waa to the first semiconductor wafer Waa. The substrate 14 has an organic substrate 90, circuit patterns 84 and 94 disposed on the organic substrate 90, and connection terminals 95 disposed on the side of the organic substrate 90 opposite to the circuit patterns 84 and 94. The first semiconductor wafer Waa is attached to the substrate 14 by an adhesive 41. A first conductive line 88 is connected to the first semiconductor wafer Waa, and the first semiconductor wafer Waa is electrically connected to the circuit pattern 84 via the first conductive line 88. A portion of the first conductive line 88 is embedded in the adhesive film 10. A second conductive line 98 is connected to the second semiconductor wafer Waa, and the second semiconductor wafer Waa is electrically connected to the circuit pattern 84 via the second conductive line 98.

[0099] The semiconductor device 201 shown in Figure 10 can be manufactured by the same method as the semiconductor device 200, which includes the step of attaching a second semiconductor wafer Waa to a first semiconductor wafer Wa by means of an adhesive film 10.

[0100] Figure 11 is a schematic cross-sectional view showing another embodiment of the semiconductor device. The semiconductor device 202 mainly comprises a substrate 14 (organic substrate 90), a first semiconductor wafer Wa and a second semiconductor wafer Waa mounted on the substrate 14, a sealing layer 42 sealing the first semiconductor wafer Waa and the second semiconductor wafer Waa, and an adhesion film 10 that embeds the first semiconductor wafer Waa and simultaneously attaches the second semiconductor wafer Waa to the substrate 14. The first semiconductor wafer Waa is a flip-chip type wafer, electrically connected to the substrate 14 via a plurality of electrodes 96. An underfill 50 is filled between the first semiconductor wafer Waa and the substrate 14. [Example]

[0101] The present disclosure will now be described in detail based on embodiments, but the present disclosure is not limited thereto.

[0102] [Preparation of the adhesive membrane] (Examples 1-7 and Comparative Examples 1-3) <Preparation of Adhesive Varnish> Cyclohexanone was added to the composition consisting of components (A) and (C) according to the product names and composition ratios (unit: parts by mass) shown in Tables 1 and 2, and the mixture was stirred. Component (B) as shown in Tables 1 and 2 was added and stirred, followed by components (D) and (E) as shown in Tables 1 and 2, and the mixture was stirred until all components were homogeneous, thus preparing the adhesive varnish. Note that the values ​​for components (B) and (C) shown in Tables 1 and 2 refer to the parts by mass of the solid components.

[0103] (A) Composition: Thermosetting resin component (A1) Composition: Thermosetting resin (A1-1)N-500P-10 (Trade name, manufactured by DIC Corporation, o-cresyl phenolic varnish type epoxy resin, epoxy equivalent: 204g / eq, softening point: 75~85℃) (A1-2) EXA-830CRP (trade name, manufactured by DIC Corporation, liquid bisphenol F epoxy resin, epoxy equivalent: 159g / eq)

[0104] (A2) Ingredients: Curing agent (A2-1)MEH-7800M (Trade name, manufactured by Meiwa Chemical Industry Co., Ltd., phenyl aralkyl type phenolic resin, hydroxyl equivalent: 174 g / eq, softening point: 80℃) (A2-2) PSM-4326 (trade name, manufactured by Gunei Chemical Co., Ltd., phenolic varnish resin, hydroxyl equivalent: 105 g / eq, softening point: 120℃)

[0105] (B) Component: Elastomer (B1) Composition: First acrylic resin (B1-1) Acrylic Resin A (an acrylic resin that is a copolymer of butyl acrylate / ethyl acrylate / ethyl methacrylate / glycidyl methacrylate / styrene, with a content of styrene structural units of 9% by mass (based on total structural units), weight average molecular weight of 400,000, and Tg of 5℃) (B2) Composition: Secondary acrylic resin (B2-1) Acrylic Resin B (HTR-860P-3CSP (trade name), manufactured by Nagase ChemteX Corporation, acrylic resin, weight average molecular weight: 800,000, Tg: 12℃) (B2-2) Acrylic resin C (an acrylic resin from SG-P3 (trade name, manufactured by Nagase ChemteX Corporation) with the structural units from acrylonitrile removed, weight average molecular weight: 600,000, Tg: 12℃)

[0106] (C) Composition: Inorganic filler (C-1) Silica filler A (SC2050-HLG (trade name), manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size: 0.50μm) (C-2) Silica filler B (silica filler dispersion, average particle size: 0.18μm)

[0107] (D) Curing accelerator (D-1)2PZ-CN (trade name, manufactured by SHIKOKU CHEMICALS CORPORATION, 1-cyanoethyl-2-phenylimidazolium)

[0108] <Preparation of Adhesive Membrane> The prepared adhesive varnish was filtered through a 100-mesh filter and then vacuum defoamed. As the substrate layer, a 38 μm thick polyethylene terephthalate (PET) film that had undergone a demolding treatment was prepared, and the vacuum-defoamed adhesive varnish was coated onto the PET film. The coated adhesive varnish was dried in two stages: first at 90°C for 5 minutes, then at 140°C for 5 minutes, to obtain the adhesive films of Examples 1-7 and Comparative Examples 1-3 in stage B. The thickness of the adhesive film was adjusted to 60 μm based on the amount of adhesive varnish applied. Two 60 μm thick adhesive films were prepared and laminated at 70°C to create an adhesive film with a thickness of 120 μm.

[0109] [Evaluation of the adhesive membrane] Measurement of the proportion of nitrile groups in acrylic resins The IR spectrum of the adhesive film from Example 3 was measured, and the PA CN / PA CO ratio was calculated. First, the transmission IR spectrum of the adhesive film was measured using the KBr ingot method, with absorbance displayed on the vertical axis and wavenumber (cm⁻¹) on the horizontal axis. An FT-IR6300 (manufactured by JASCO Corporation, light source: high-brightness ceramic light source, detector: DLATGS) was used for the IR spectrum measurement. Next, the area of ​​absorbance enclosed by the spectrum and the line connecting the two points at 1650 cm⁻¹ and 1800 cm⁻¹ on the spectrum was calculated as PA CO. Similarly, the area of ​​absorbance enclosed by the spectrum and the line connecting the two points at 2230 cm⁻¹ and 2300 cm⁻¹ on the spectrum was calculated as PA CN. Based on the calculated PA CO and PA CN, the PA CN / PA CO ratio was determined. This operation was performed three times, and the average of the three PA CN / PA CO ratios was calculated, resulting in a value of 0.014.

[0110] <Evaluation of HAST resistance> A printed circuit board substrate (manufactured by Showa Denko Materials co., Ltd., trade name: MCL-E-679) was prepared by laminating a 70 μm thick copper foil onto a glass epoxy substrate. The copper surface of the printed circuit board substrate was etched to form a comb-shaped electrode with a line / space ratio of 40 μm / 40 μm. Adhesive films (5 mm × 12 mm) of Examples 1-7 and Comparative Examples 1-3, each with a thickness of 120 μm, were attached to the substrate on which the comb-shaped electrode was formed, at a temperature of 120°C, a time of 2 seconds, and a pressure of 0.2 MPa. Next, an evaluation substrate was prepared by heating the substrate in a vacuum dryer at a temperature of 90°C, a time of 1 hour, and a pressure of 0.6 MPa, followed by heating at a temperature of 130°C, a time of 1 hour, and a pressure of 0.6 MPa. The evaluation substrate was exposed at 130°C and 85% RH with a DC voltage of 13.2 V applied, and the resistance between the lines was measured. In the resistance measurement, the number of times a resistance decrease of more than two digits was observed was calculated, and the time from the start of the experiment to the observation of the 50th resistance decrease was evaluated according to the following criteria. The results are shown in Tables 1 and 2. A: The time from the start of the experiment to the observation of the 50th decrease in resistance value exceeded 100 hours. B: The time from the start of the experiment to the observation of the 50th decrease in resistance value is more than 50 hours but less than 100 hours. C: The time from the start of the experiment to the observation of the 50th decrease in resistance value is less than 50 hours.

[0111] <Evaluation of the retention force> (Fabrication of semiconductor wafers with adhesive films) A dicing film (manufactured by Showa Denko Materials Co., Ltd., 100 μm thick) having a resin film and an adhesive layer was prepared. Adhesive films (120 μm thick) from Examples 1-7 and Comparative Examples 1-3 were then attached to the dicing film, respectively, to create a die-bonding integrated film comprising the dicing film and an adhesive film disposed on one side of the dicing film. Next, a semiconductor wafer (400 μm thick) was attached to the adhesive film side of the die-bonding integrated film at a stage temperature of 70°C. The wafer was then cut using a fully automatic dicing machine DFD-6361 (manufactured by DISCO Corporation) to form a semiconductor wafer with dimensions of 2 mm × 2 mm. A semiconductor wafer with an adhesive film was obtained by picking up the semiconductor wafer and the adhesive film attached thereto.

[0112] (Adhesion to organic substrate (solder resist)) The shear strength of the cured semiconductor wafer was measured using the obtained adhesive film. The semiconductor wafer was thermo-pressed onto a solder resist (TAIYO HOLDINGS CO.,LTD., trade name: SR-1). The pressing conditions were: temperature 120°C, time 1 second, and pressure 0.1 MPa. The evaluation sample obtained by pressing was then placed in a desiccator and cured by heating at 110°C for 1 hour, followed by a 30-minute temperature increase, and finally at 175°C for 5 hours. The cured evaluation sample was then subjected to shear strength testing using a universal bonding strength tester (Nordson Advanced Technology KK, trade name: Series 4000) to hold and stretch the semiconductor wafer, thereby measuring the shear strength of the cured semiconductor wafer and organic substrate. The wafer shear strength was measured at 6.7 MPa, 260°C, and a holding time of 20 seconds. The results are shown in Tables 1 and 2.

[0113] (Adhesion to the gold substrate) The adhesion was evaluated using a gold substrate, which is less adhesive to organic substrates. In other words, the adhesion to the gold substrate was evaluated under more stringent conditions than the adhesion to the organic substrate (solder resist). The shear strength of the cured semiconductor wafer was measured using the obtained semiconductor wafer with the adhesive film. The semiconductor wafer was thermo-pressed onto the gold substrate. The pressing conditions were: temperature 120°C, time 1 second, and pressure 0.1 MPa. The evaluation sample obtained by pressing was then placed in a desiccant and heated at 110°C for 1 hour, followed by a 30-minute temperature increase, and then heated at 175°C for 5 hours to cure it. Next, the cured evaluation sample was subjected to shear strength testing using a universal bonding strength tester (Nordson Advanced Technology KK, product name: Series 4000) to hold and stretch the semiconductor wafer, thereby measuring the shear strength of the cured semiconductor wafer and gold substrate. The wafer shear strength was measured under conditions of 6.7 MPa, 260°C, and a stage holding time of 20 seconds. The results are shown in Tables 1 and 2. Additionally, in Comparative Example 1, the shear strength of the wafer was below the lower limit of the measuring device and could not be measured.

[0114] [Table 1] Example 1 Example 2 Comparative Example 1 (A) (A1) (A1-1) 15 15 15 (A1-2) 14 14 14 (A2) (A2-1) twenty four twenty four twenty four (A2-2) - - - (B) (B1) (B1-1) 9 17 - (B2) (B2-1) 9 - - (B2-2) - - 17 (C) (C-1) 29 29 29 (C-2) - - - (D) (D-1) 0.06 0.06 0.06 HAST resistance A A A Then force (Crystal shear strength, MPa) organic substrate 6.2 3.6 3.0 gold substrate 1.0 1.0 NG

[0115] As shown in Table 1, the adhesive films of Examples 1 and 2, which contain acrylic resin with structural units derived from monomers having aromatic rings as elastomers, exhibit excellent HAST resistance and superior adhesion compared to the adhesive film of Comparative Example 1, which does not contain acrylic resin with structural units derived from monomers having aromatic rings as elastomers.

[0116] [Table 2] Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 2 Comparative Example 3 (A) (A1) (A1-1) 15 15 5 15 10 15 10 (A1-2) 8 13 10 5 5 14 17 (A2) (A2-1) 5 5 5 5 5 twenty four - (A2-2) 10 10 5 5 5 - 12 (B) (B1) (B1-1) 10 19 18 10 12 - - (B2) (B2-1) 26 19 twenty four 10 12 17 twenty two (B2-2) - - - - - - - (C) (C-1) 14 10 twenty two 40 27 29 39 (C-2) 13 10 10 10 twenty three - - (D) (D-1) 0.06 0.06 0.06 0.06 0.06 0.06 0.06 HAST resistance B B A B B C C Next force (MPa) gold substrate 4.6 3.3 3.0 4.3 3.9 1.0 1.8

[0117] As shown in Table 2, the adhesive films of Examples 3 to 7, which contain acrylic resin with structural units derived from monomers having aromatic rings as elastomers, exhibit superior HAST resistance and adhesion compared to the adhesive films of Comparative Examples 2 and 3, which do not contain acrylic resin without structural units derived from monomers having aromatic rings as elastomers.

[0118] The results above confirm that the semiconductor adhesive film disclosed herein has excellent HAST resistance and high adhesion.

[0119] 10: Adhesive membrane 14:Substrate 20: Substrate layer (cutting film) 30: Protective film 41: Adhesive 42: Sealing layer 84, 94: Circuit patterns 88: First conductor 90: Organic substrate 98: Second conductor 100, 110: Laminated bodies 200, 201, 202: Semiconductor devices Wa: First Semiconductor Chip Waa: Second semiconductor chip

Claims

1. An adhesive film for semiconductors, comprising a thermosetting component, an elastomer, and an inorganic filler, wherein the elastomer comprises an acrylic resin having structural units derived from monomers having aromatic rings, and the acrylic resin having structural units derived from monomers having aromatic rings has a weight average molecular weight of 100,000 or more.

2. The semiconductor adhesive film as described in claim 1, having a thickness of 60 to 150 μm.

3. The semiconductor bonding film as described in claim 1 or claim 2, used to bond a semiconductor wafer to a substrate while embedding other semiconductor wafers.

4. The semiconductor adhesive film as described in claim 1, having a thickness of 25 to 80 μm.

5. The semiconductor bonding film as described in claim 1 or claim 4, used to bond a semiconductor wafer to the aforementioned other semiconductor wafer while embedding a portion or all of a wire for connection to other semiconductor wafers.

6. The semiconductor adhesive film as described in any one of claims 1, 2 and 4, wherein the elastomer further comprises an acrylic resin that does not have structural units derived from monomers having aromatic rings, wherein the weight average molecular weight of the acrylic resin that does not have structural units derived from monomers having aromatic rings is 500,000 or more.

7. The semiconductor adhesive film as described in any one of claims 1, 2 and 4, wherein the content of the aforementioned elastomer is 10 to 60% by mass based on the total amount of the semiconductor adhesive film.

8. The semiconductor adhesive film as described in any one of claims 1, 2 and 4, wherein the content of the inorganic filler is 30 to 250 parts by mass relative to 100 parts by mass of the aforementioned thermosetting component.

9. A die-cutting bonding integral film comprising: a dicing film; and a semiconductor bonding film disposed on the aforementioned dicing film according to any one of claims 1, 2 and 4.

10. A method for manufacturing a semiconductor device, comprising the step of attaching a second semiconductor wafer to a substrate on which a first semiconductor wafer is mounted by means of a semiconductor adhesive film as described in claim 1 or claim 2, wherein the first semiconductor wafer is embedded in the aforementioned adhesive film.

11. A method of manufacturing a semiconductor device, comprising the step of attaching a second semiconductor wafer to a first semiconductor wafer by means of a semiconductor adhesive film as described in claim 1 or claim 4, wherein a wire is connected to the first semiconductor wafer, and a portion or all of the wire is embedded in the adhesive film.

12. A method for manufacturing a semiconductor device as described in claim 10, wherein the aforementioned first semiconductor wafer is a controller wafer.

13. A method for manufacturing a semiconductor device as described in claim 11, wherein the aforementioned first semiconductor wafer is a controller wafer.

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