Film-shaped adhesive, cutting grain bonding integrated film, and semiconductor device and manufacturing method thereof

Abstract

Disclosed is a film-shaped adhesive. The film-shaped adhesive contains a thermosetting resin, a curing agent, and an elastomer. The thermosetting resin contains an epoxy resin having a fluorene skeleton.

Description

Technical Field

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

[0002] In the semiconductor field, represented by data storage media and integrated circuits (ICs), semiconductor packaging has been increasingly becoming more dense and integrated in recent years, driven by higher functionality. Consequently, the thinning of semiconductor wafers has progressed, but this process can easily lead to defects such as wafer breakage, sometimes resulting in reduced yield. Therefore, as the thickness of semiconductor wafers decreases (e.g., below 50 μm), there is a growing shift from traditional physical grinding methods to new processing techniques.

[0003] As a novel processing method, a method has been proposed in recent years that involves irradiating the interior of a semiconductor wafer along a predetermined cutting line with a laser beam to form a modified region, and then cutting the semiconductor wafer by extending the outer periphery (e.g., Patent Documents 1 and 2). This method is called Stealth Dicing. Along with the development of new processing methods, there is a need to develop semiconductor materials suitable for this purpose. As such semiconductor materials, die-gluing integrated films combining the properties of dicing strips and die-bonding films have been reported (e.g., Patent Documents 3 and 4).

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2002-192370

[0007] Patent Document 2: Japanese Patent Application Publication No. 2003-338467

[0008] Patent Document 3: Japanese Patent Application Publication No. 2015-211080

[0009] Patent Document 4: Japanese Patent Application Publication No. 2016-115775 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] However, in semiconductor device manufacturing processes, when dividing the material by forming modified regions through stealth laser cutting, cooling expansion (hereinafter sometimes referred to as "cooling expansion") is sometimes performed. However, when applying conventional die-bonding monolithic films to cooling expansion, undivided adhesive layers formed by the film-like adhesive sometimes occur. If undivided adhesive layers occur, reduced yield and decreased production time efficiency for screening undivided products become problems.

[0012] On the other hand, as semiconductor wafers become thinner, they become more prone to warping, sometimes causing the adhesive layer formed by the film adhesive to easily peel off from the semiconductor wafer. Therefore, the film adhesive is required to have excellent separability based on cooling expansion, and also excellent adhesion to the semiconductor wafer.

[0013] As a method to improve slitting performance, increasing the amount of inorganic filler incorporated in the film adhesive is known. However, in this case, the film adhesive becomes too brittle, sometimes resulting in problems such as debris scattering during slitting and decreased adhesion between the adhesive layer and the semiconductor wafer.

[0014] As another method to improve separability, it is also known to use materials with high glass transition temperature (Tg) or low molecular weight materials as elastomers, but the adhesion is not greatly improved in these methods.

[0015] Therefore, the main objective of this invention is to provide a film adhesive that exhibits excellent segmentation based on cooling expansion and excellent adhesion to semiconductor wafers.

[0016] means for solving technical problems

[0017] One aspect of the present invention relates to a film-like adhesive. This film-like adhesive comprises a thermosetting resin, a curing agent, and an elastomer. The thermosetting resin comprises an epoxy resin having a fluorene backbone. According to such a film-like adhesive, it exhibits excellent segmentation properties due to cooling expansion and also excellent adhesion to semiconductor wafers.

[0018] Film-like adhesives may also contain inorganic fillers.

[0019] The thickness of the film adhesive can be less than 20 μm.

[0020] Film-like adhesives can be used in the manufacturing process of semiconductor devices composed of multiple stacked semiconductor elements. In this case, the semiconductor device can be a stacked MCP (Multi-Chip Package) composed of multiple layers of semiconductor elements (semiconductor wafers), or a three-dimensional NAND flash memory.

[0021] Another aspect of the present invention relates to a grain-joining integrated film. This grain-joining integrated film sequentially comprises a substrate layer, a pressure-sensitive adhesive layer, and an adhesive layer formed from the aforementioned film-like adhesive.

[0022] Another aspect of the present invention relates to a semiconductor device. The semiconductor device includes: a semiconductor element; a support member for mounting the semiconductor element; and an adhesive member disposed between the semiconductor element and the support member, for bonding the semiconductor element and the support member. The adhesive member is a cured product of the aforementioned film adhesive. The semiconductor device may also include other semiconductor elements laminated on the surface of the semiconductor element.

[0023] Another aspect of the present invention relates to a method for manufacturing a semiconductor device. One aspect of the method for manufacturing the semiconductor device includes: bonding the semiconductor element to the support member or the first semiconductor element to the second semiconductor element by distributing the aforementioned film adhesive between a semiconductor element and a support member or between a first semiconductor element and a second semiconductor element.

[0024] Other methods of manufacturing the semiconductor device include: a step of attaching a semiconductor wafer to an adhesive layer of the aforementioned die-bonding monolithic film; a step of dicing the semiconductor wafer with the adhesive layer attached; a step of fabricating a plurality of monolithic semiconductor elements with adhesive sheets by expanding a substrate layer under cooling conditions; a step of picking up the semiconductor elements with adhesive sheets from the pressure-sensitive adhesive layer; and a step of bonding the picked-up semiconductor elements with adhesive sheets to a support member via adhesive sheets. The method of manufacturing the semiconductor device may further include a step of bonding other semiconductor elements with adhesive sheets to the surface of the semiconductor element bonded to the support member via adhesive sheets.

[0025] Invention Effects

[0026] According to the present invention, a film-like adhesive is provided that exhibits excellent segmentation based on cooling expansion and excellent adhesion to semiconductor wafers. Furthermore, according to the present invention, a die-bonding integral film using such a film-like adhesive, a semiconductor device, and a method for manufacturing the same are provided. Moreover, according to the present invention, a method for manufacturing a semiconductor device using such a die-bonding integral film is provided. Attached Figure Description

[0027] Figure 1 This is a schematic cross-sectional view illustrating one embodiment of a film-like adhesive.

[0028] Figure 2 It is a three-dimensional view schematically representing the state of the specimen fixed on the fixture during a cutting test.

[0029] Figure 3It is a cross-sectional view schematically representing the state in which a load is applied to the specimen by pressing in a clamp during a cutting test.

[0030] Figure 4 This is a graph that schematically represents an example of the results of a cutting test.

[0031] Figure 5 This is a schematic cross-sectional view illustrating one embodiment of a grain-jointed integral film.

[0032] Figure 6 This is a schematic cross-sectional view illustrating one embodiment of a semiconductor device.

[0033] Figure 7 This is a schematic cross-sectional view illustrating another embodiment of a semiconductor device.

[0034] Figure 8 This is a schematic cross-sectional view illustrating another embodiment of a semiconductor device. Detailed Implementation

[0035] Hereinafter, embodiments of the present invention will be described with appropriate reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below. In the embodiments described below, unless specifically stated otherwise, the constituent elements (including processes, etc.) are not essential. The sizes of the constituent elements in each figure are conceptual sizes, and the relative sizes of the constituent elements are not limited to the relationships shown in the figures.

[0036] The numerical values ​​and their ranges in this invention are the same and do not limit the invention. In this specification, the numerical range indicated by "~" represents the range encompassed by the values ​​before and after "~" as the minimum and maximum values, respectively. Within the numerical ranges described in stages 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 stages. Furthermore, within the numerical ranges described in this specification, the upper or lower limit of that numerical range can also be replaced by the values ​​shown in the embodiments.

[0037] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar terms such as (meth)acryloyl, (meth)acrylic copolymers, etc.

[0038] Unless otherwise specified, each ingredient and material listed in this instruction manual may be used alone or in combination with two or more.

[0039] [Film adhesive]

[0040] Film adhesives contain thermosetting resins (hereinafter, sometimes referred to as "component (A)"), curing agents (hereinafter, sometimes referred to as "component (B)"), and elastomers (hereinafter, sometimes referred to as "component (C)"). In addition to components (A), (B), and (C), film adhesives may also contain inorganic fillers (hereinafter, sometimes referred to as "component (D)"), coupling agents (hereinafter, sometimes referred to as "component (E)"), curing accelerators (hereinafter, sometimes referred to as "component (F)"), and other components.

[0041] Film-like adhesives can be obtained by forming an adhesive composition containing component (A), component (B), and component (C), as well as other components ((D), (E), (F), and other components, etc.) as needed, into a film. The film-like adhesive (adhesive composition) can also pass through a semi-cured (stage B) state and become a fully cured (stage C) state after a curing treatment.

[0042] (A) Composition: Thermosetting resin

[0043] From an adhesive point of view, component (A) may contain epoxy resin, or may be formed from one or more epoxy resins. Film adhesives contain an epoxy resin with a fluorene backbone (hereinafter, sometimes referred to as "component (A1)") as component (A).

[0044] The (A1) component is a compound having a fluorene framework within its molecule and possessing epoxy groups. Compounds containing the (A1) component can be used without particular limitation as long as they meet these conditions. By using a thermosetting resin containing the (A1) component, the film adhesive can become an adhesive with excellent segmentation based on cooling expansion and excellent adhesion to semiconductor wafers. The inventors of this invention believe that this effect is achieved for the following reasons: The fluorene framework has a rigid structure with a large three-dimensional volume, therefore it is presumed that molecules of other materials can enter the gaps in the structure. Therefore, it is believed that the (A1) component is relatively easy to mix with elastomers (e.g., acrylic rubber), easily modifying the properties of this elastomer from a soft and difficult-to-cut material to a hard and easy-to-cut material. Along with this, it is believed that by increasing the elastic modulus, the adhesion to semiconductor wafers is also improved.

[0045] (A1) Components may be, for example, epoxy resins represented by the following general formula (X).

[0046]

[0047] In equation (X), Z 1 and Z 2 Each of these groups independently represents a divalent aromatic hydrocarbon group. Z 1 and Z 2They can be the same or different, but they can be the same. Examples of divalent aromatic hydrocarbon groups include groups that remove two hydrogen atoms directly bonded to the carbon atoms constituting the ring from monocyclic aromatic hydrocarbons (e.g., benzene) or polycyclic aromatic hydrocarbons (e.g., dicyclic aromatic hydrocarbons such as naphthalene and indene; tricyclic aromatic hydrocarbons such as anthracene, phenanthrene, dihydrophenanthrene, and fluorene; tetracyclic aromatic hydrocarbons such as benzo[a]anthracene, benzo[a]phenanthrene, benzo[a]fluorene, pyrene, and benzo[a]acenaphthene). Divalent aromatic hydrocarbon groups include groups that remove two hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon formed by linking multiple of these aromatic hydrocarbons (e.g., biphenyl diyl, terphenyl diyl, etc.). Divalent aromatic hydrocarbon groups can be phenyldiyl (phenylene) or naphthyl (naphthylene).

[0048] The fluorene skeleton in epoxy resin represented by formula (X), and the fluorene skeleton represented by Z 1 and Z 2 The divalent aromatic hydrocarbon group can also have substituents. Examples of substituents include alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl; acyl groups such as acetyl, propionyl, and benzoyl; alkoxy groups such as methoxy, ethoxy, propoxy, and isopropoxy; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; cyano; carboxyl; nitro; amino; substituted amino groups (e.g., monoalkyl or dialkylamino groups); halogen atoms such as fluorine and chlorine atoms, etc.

[0049] In equation (X), R 1A and R 2A Each of the following can be used independently to represent an alkylene group having 1 to 10 carbon atoms. R 1A and R 2A They can be the same or different, but they can be the same. Examples of alkylenes include methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, and other straight-chain or branched alkylenes with 1 to 10 carbon atoms. Alkylenes can be alkylenes with 2 to 6 carbon atoms, or they can be alkylenes with 2 or 3 carbon atoms.

[0050] In equation (X), p1 and p2 independently represent integers greater than or equal to 0. p1 and p2 can be the same or different, but they can also be the same. p1 and p2 can be integers from 0 to 4 or integers from 1 to 4.

[0051] In equation (X), R 1B R 1C R 1D R 1E R 1F R 2B R 2C R 2D R 2E and R 2FEach can be independently represented by either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 1B R 1C R 1D R 1E R 1F R 2B R 2C R 2D R 2E and R 2F They can be the same or different. Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. R 1B R 1C R 1D R 1E R 1F R 2B R 2C R 2D R 2E and R 2F It can be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or it can be a hydrogen atom.

[0052] Commercially available epoxy resins represented by the general formula (X) include, for example, PG-100, EG-200, and CG-500 (trade names, all manufactured by Osaka Gas Chemicals Co., Ltd.).

[0053] There is no particular limitation on the epoxy equivalent of component (A1), which can be 80–600 g / eq, 100–500 g / eq, or 200–400 g / eq. When the epoxy equivalent of component (A1) is within such a range, there is a tendency to obtain better reactivity and flowability.

[0054] Based on the total mass of component (A), the content of component (A1) can be 40 to 100% by mass. When the content of component (A1) is within such a range, the effects of the present invention tend to be more significant. Based on the total mass of component (A), the content of component (A1) can be 50% or more by mass, 60% or more by mass, 70% or more by mass, or 80% or more by mass.

[0055] Based on the total mass of the film adhesive, the content of component (A1) can be 1% or more by mass, 3% or more by mass, or 5% or more by mass, or less than 30% by mass, 20% or less by mass, or less than 15% by mass. Based on the total mass of the film adhesive, when the content of component (A1) is 1% or more by mass, it tends to have a better elastic modulus after curing. Based on the total mass of the film adhesive, when the content of component (A1) is 30% or less by mass, it tends to have better flexibility before curing.

[0056] In addition to component (A1), component (A) may also contain epoxy resins that do not have a fluorene backbone in the molecule (hereinafter, sometimes referred to as "component (A2)"). Examples of component (A2) include, for instance, 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; zirconia type epoxy resin; epoxy resin containing a triazine backbone; triphenol methane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; biphenyl aralkyl type epoxy resin; naphthalene type epoxy resin; diglycidyl ether compounds of polycyclic aromatic compounds such as polyfunctional phenols and anthracene. Component (A2) may also contain cresol varnish type epoxy resin.

[0057] There is no particular limitation on the epoxy equivalent of component (A2), which can be 80–600 g / eq, 100–500 g / eq, or 200–400 g / eq. When the epoxy equivalent of component (A1) is within such a range, there is a tendency to obtain better reactivity and flowability.

[0058] Based on the total mass of component (A), the content of component (A2) can be 0 to 60% by mass. Based on the total mass of component (A), the content of component (A2) can also be less than 50% by mass, less than 40% by mass, less than 30% by mass, or less than 20% by mass.

[0059] Based on the total mass of the film adhesive, the content of component (A) can be 1% or more by mass, 3% or more by mass, or 5% or more by mass, or less than 30% by mass, 20% or less by mass, or less than 15% by mass. Based on the total mass of the film adhesive, when the content of component (A) is 1% or more by mass, it tends to have a better elastic modulus after curing. Based on the total mass of the film adhesive, when the content of component (A) is 30% or less by mass, it tends to have better flexibility before curing.

[0060] (B) Component: Curing agent

[0061] The curing agent used as component (A) can be a commonly used curing agent. If component (A) contains epoxy resin (formed from one or more epoxy resins), then component (B) can be, for example, phenolic resin, ester compound, aromatic amine, aliphatic amine, acid anhydride, etc. From the viewpoint of reactivity and stability over time, component (B) can be a phenolic resin.

[0062] Phenolic resins can be used without particular restrictions as long as they contain phenolic hydroxyl groups within the molecule. Examples of phenolic resins 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 synthesized from allylated bisphenol A, allylated bisphenol F, allylated naphthalene glycol, phenolic varnish, phenols such as phenol and / or naphthols with dimethoxy-p-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl type phenolic resins; and phenyl aralkyl type phenolic resins.

[0063] The hydroxyl equivalent of phenolic resin can be above 70 g / eq or between 70 and 300 g / eq. When the hydroxyl equivalent of phenolic resin is above 70 g / eq, it tends to further increase the storage modulus. When it is below 300 g / eq, it can prevent adverse conditions caused by foaming, gas release, etc.

[0064] The softening point of phenolic resin can be above 90℃, or above 95℃, 100℃, 105℃, 110℃, or 115℃. The upper limit of the softening point of phenolic resin can be, for example, below 200℃. Furthermore, the softening point refers to the value measured according to JIS K7234 using the ring and ball method.

[0065] Based on the total mass of the film adhesive, the content of component (B) can be more than 1%, more than 2%, or more than 3%, or less than 20%, less than 15%, or less than 10%.

[0066] When component (A) is epoxy resin and component (B) is 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 of epoxy resin / hydroxyl equivalent of phenolic resin) can be 0.30 / 0.70 to 0.70 / 0.30, 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45. When this equivalent ratio is 0.30 / 0.70 or higher (epoxy equivalent of epoxy resin is 0.30 or higher), there is a tendency to obtain more sufficient curability. When this equivalent ratio is 0.70 / 0.30 or lower (epoxy equivalent of epoxy resin is 0.70 or lower), it is possible to prevent the viscosity from becoming too high and to obtain more sufficient flowability.

[0067] Based on the total mass of the film adhesive, the combined content of component (A) and component (B) can be 1% or more by mass, 5% or more by mass, or 10% or more by mass. When the combined content of component (A) and component (B) is within such a range, there is a tendency for further improvement in adhesiveness. From an operational point of view, based on the total mass of the film adhesive, the combined content of component (A) and component (B) can be 40% or less by mass, 30% or less by mass, or 20% or less by mass.

[0068] (C) Component: Elastomer

[0069] Examples of components (C) include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, and butadiene resins; as well as modified forms of these resins. These can be used alone or in combination of two or more. Component (C) is particularly advantageous because it contains fewer ionic impurities, exhibits superior heat resistance, and better ensures reliable connections in semiconductor devices. It also has superior flowability, and therefore can be an acrylic resin (acrylic rubber) with (meth)acrylate constituent units as its main component. Based on the total amount of constituent units, the content of (meth)acrylate constituent units in component (C) can be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The acrylic resin (acrylic rubber) may contain constituent units derived from (meth)acrylate having crosslinking functional groups such as epoxy groups, alcoholic or phenolic hydroxyl groups, and carboxyl groups.

[0070] The glass transition temperature (Tg) of component (C) can be 5°C or higher, or 10°C or higher. When the Tg of component (C) is 5°C or higher, the adhesion of the film adhesive can be further improved, thus preventing the film adhesive from becoming too flexible. Therefore, the film adhesive is easily cut during wafer dicing, preventing burrs. There is no particular upper limit to the Tg of component (C), 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 component (C) is below 55°C, it tends to suppress the decrease in the flexibility of the film adhesive. Therefore, when the film adhesive is attached to the semiconductor wafer, it tends to be easily and sufficiently embedded in the gaps. Furthermore, it can prevent chipping during dicing due to decreased adhesion to the semiconductor wafer. Here, the glass transition temperature (Tg) refers to the value measured using a DSC (Differential Scanning Calorimeter) (e.g., Rigaku Corporation's ThermoPlus 2). By adjusting the type and content of the constituent units of component (C) (in the case of acrylic resin (acrylic rubber), the constituent units derived from (meth)acrylates), the Tg of component (C) can be adjusted to the desired range.

[0071] The weight-average molecular weight (Mw) of component (C) can be above 100,000, above 300,000, or above 500,000, and can be below 3 million, below 2 million, or below 1 million. When the Mw of component (C) is within such a range, film formation properties, film strength, flexibility, tack, etc., can be appropriately controlled, and reflow properties are excellent, which can improve embedding performance. Here, Mw refers to the value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0072] Commercially available products that are (C) ingredients include SG-P3, SG-80H (both manufactured by Nagase ChemteX Corporation), and KH-CT-865 (manufactured by Hitachi Chemical Co., Ltd.).

[0073] Based on the total mass of the film adhesive, the content of component (C) can be 30% or more, 40% or more, or 45% or more by mass. When the content of component (C) is within this range, there is a tendency for better film coating properties. Based on the total mass of the film adhesive, the content of component (C) can be less than 80% by mass, less than 70% by mass, or less than 65% by mass. When the content of component (C) is within this range, the content of components (A) and (B) can be adequately ensured, and there is a tendency to take into account other properties.

[0074] (D) Composition: Inorganic filler

[0075] Examples of components (D) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate crystals, boron nitride, and silicon dioxide. These can be used alone or in combination of two or more. From the viewpoint of adjusting melt viscosity, component (D) can also be silicon dioxide. The shape of component (D) is not particularly limited and can be spherical.

[0076] From the viewpoint of fluidity and storage modulus, the average particle size of component (D) can be 0.7 μm or less, or 0.6 μm or less, or 0.5 μm or less. The average particle size of component (D) can, for example, be 0.01 μm or more. Here, average particle size refers to the average particle size determined by dynamic light scattering. Alternatively, the average particle size of component (D) can also be determined by using a film-like adhesive containing component (D). In this case, the residue obtained by decomposing the resin component through heating the film-like adhesive is dispersed in a solvent to prepare a dispersion, and the average particle size of component (D) can be determined based on the particle size distribution obtained by applying dynamic light scattering to it.

[0077] Based on the total mass of the film adhesive, the content of component (D) can be 60% by mass or less, 50% by mass or less, or 45% by mass or less. When the content of component (D) is within such a range, there is a tendency for better film coating properties. Based on the total mass of the film adhesive, the content of component (D) can be 10% by mass or more, 15% by mass or more, or 20% by mass or more.

[0078] (E) Component: Coupling agent

[0079] (E) Component can also be a silane coupling agent. Examples of silane coupling agents include γ-ureopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0080] (F) Ingredients: Curing accelerator

[0081] Examples of components (F) 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 (F) can be imidazoles and their derivatives.

[0082] 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.

[0083] Film-like adhesives may also contain other components. Examples of such components include pigments, ion scavengers, and antioxidants.

[0084] Based on the total mass of the film adhesive, the total content of component (E), component (F) 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 20% by mass, less than 10% by mass or less than 5% by mass.

[0085] Figure 1 This is a schematic cross-sectional view illustrating one embodiment of a film-like adhesive. Figure 1 The film-like adhesive 1 shown is formed by shaping an adhesive composition into a film. The film-like adhesive 1 can typically be in a semi-cured (stage B) state and, after a curing treatment, become fully cured (stage C) in a completely cured state. The film-like adhesive 1 can be formed by applying the adhesive composition onto a support film. In the formation of the film-like adhesive 1, a varnish of the adhesive composition (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), as well as any other components added as needed, in a solvent. The resulting adhesive varnish is then applied onto a support film, and the solvent is removed by heating and drying, thereby obtaining the film-like adhesive 1.

[0086] The supporting film is not particularly limited as long as it can withstand the aforementioned heating and drying process. 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 has been treated with silicone-based, silica-based, or other release agents. The thickness of the supporting film can be, for example, 10–200 μm or 20–170 μm.

[0087] Mixing or kneading can be done using common mixers, pounders, three-roll mills, ball mills, and other dispersants, and these can be combined appropriately.

[0088] 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.

[0089] 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. Heat drying is not particularly limited as long as the solvent used is sufficiently evaporated, and can be carried out at a heating temperature of 50–150°C for a heating time of 1–30 minutes. Heat drying can be carried out in stages at different heating temperatures and for different heating times.

[0090] The thickness of the film adhesive can be less than 20 μm, or less than 18 μm, 15 μm, 12 μm, or 10 μm. There is no particular limitation on the lower limit of the thickness of the film adhesive; for example, it can be greater than 1 μm.

[0091] From the viewpoint of preventing damage or contamination, the film-like adhesive formed on the support film can also have a cover film on the side of the film-like adhesive opposite to the support film. Examples of cover films include polyethylene films, polypropylene films, and surface-removing agent treated films. The thickness of the cover film can be, for example, 15–200 μm or 30–170 μm.

[0092] Because film-like adhesives can achieve thin-film formation, they are preferably used in the manufacturing process of semiconductor devices composed of multiple stacked semiconductor elements. In this case, the semiconductor device can be a stacked MCP or a three-dimensional NAND flash memory.

[0093] In the segmentation evaluation method for the results of the cutting test under the following conditions (segmentation evaluation method for film adhesives under low temperature conditions (e.g., the range of -15°C to 0°C) with cooling expansion), the film adhesive 1 can be a film adhesive with a cutting coefficient m of 70 or less.

[0094] <Conditions>

[0095] Sample width: 5mm

[0096] Length of the sample: 23mm

[0097] Relative speed between the press-in fixture and the sample: 10 mm / min

[0098] The following describes the cut-through test. The cut-through test is classified as a flexural strength test and involves pressing the center of the specimen into the center while both ends are fixed until the specimen breaks. For example... Figure 2As shown, the specimen S is used for a cutting test while being held and fixed by a pair of specimen fixing clamps 20. The pair of specimen fixing clamps 20 are, for example, made of thick paper with sufficient strength, and each has a rectangular opening 20a in the center. A load is applied to the central portion of the fixed specimen S using a pressing clamp 21 (see reference). Figure 3 ).

[0099] Specimen S can be any cut sample of the film-like adhesive being evaluated, or it can be prepared by cutting multiple adhesive sheets from the film-like adhesive without stacking them. That is, the thickness of specimen S can also be the same as the thickness of the film-like adhesive. The width of specimen S ( Figure 2 The width (Ws) in the measurement device can be, for example, 1–30 mm, or 3–8 mm. It can be set to an appropriate width based on the conditions of the measuring device. The length of the sample S ( Figure 2 The length of the specimen S (Ls) is, for example, 5–50 mm, or 10–30 mm or 6–9 mm. The length of the specimen S depends on the size of the opening 20a of the specimen clamp 20. In addition, the shape of the specimen clamp 20 and the size of the specimen S can be other than those mentioned above, as long as the cutting test can be performed.

[0100] The press-fit clamp 21 is formed from a cylindrical component having a conical tip 21a. The diameter of the press-fit clamp 21 ( Figure 3 The radius (R) in the figure is, for example, 3–15 mm, or 5–10 mm. The angle of the tip 21a (…). Figure 3 The θ in the figure can be, for example, 40–120°, or 60–100°.

[0101] The cutting test is conducted in a thermostatic bath set to a specific temperature. The thermostatic bath only needs to be set to a constant temperature within the range of -15°C to 0°C (the assumed temperature for cooling expansion). For example, an AETEC Co., Ltd. TLF-R3-FW-PL-S thermostatic bath can be used. Using an automatic stereoscopic plotter (e.g., an A&D Company AZT-CA01 with a 50N force sensor in compression mode), the cutting work W, cutting strength P, and cutting elongation L are obtained.

[0102] The relative speed between the pressing clamp 21 and the sample S is, for example, 1–100 mm / min, or 5–20 mm / min. If the relative speed is too fast, there is a tendency to not obtain sufficient data on the cutting process; if it is too slow, there is a tendency for stress to be relaxed and difficult to cut. The pressing distance of the pressing clamp 21 is, for example, 1–50 mm, or 5–30 mm. If the pressing distance is too short, there is a tendency for it to be difficult to cut. For the film adhesive being evaluated, it is preferable to prepare multiple samples and perform multiple cutting tests to confirm the stability of the test results.

[0103] Figure 4 This is a graph representing an example of the results of a cutting test. For example... Figure 4 As shown, the cutting work W is the area enclosed in the graph plotted with the load on the vertical axis and the indentation depth until specimen S breaks on the horizontal axis. The cutting strength P is the load at which specimen S breaks. The cutting elongation L is the elongation of specimen S at the time of breakage. The cutting elongation L can be calculated using trigonometric functions based on the indentation distance at which specimen S breaks and the width of the opening 20a of the specimen fixing clamp 20.

[0104] Based on the cutting work W (N·mm), cutting strength P (N), and cutting elongation L (mm) obtained from the cutting test, the cutting coefficient m (dimensionless) and cutting resistance R (N / mm) are calculated using equations (1) and (2). 2 ).

[0105] m=W / [1000×(P×L)] (1),

[0106] R = P / A(2),

[0107] According to the research of the inventors, when a cutting test is performed under the following conditions, a film adhesive with a cutting coefficient m of 70 or less tends to have excellent segmentation properties when actually performing cooling expansion in stealth laser cutting.

[0108] <Conditions>

[0109] Sample width: 5mm

[0110] Length of the sample: 23mm

[0111] Relative speed between the press-in fixture and the sample: 10 mm / min

[0112] The cutting factor m (dimensionless) can be 70 or less, or 60 or less, 57 or less, or 55 or less. The cutting factor m is a parameter related to the tensile properties of the film adhesive under low-temperature conditions. When the cutting factor m is 70 or less, the film adhesive tends to have sufficient segmentation based on cooling expansion due to its appropriate tensile properties. The smaller the value of the cutting factor m, the more significant this tendency. The cutting factor m (dimensionless) can exceed 0, or be 10 or more, or 15 or more. When the cutting factor m is 15 or more, it tends to have good stress propagation properties. Film adhesives with cutting factors m within such a range are preferably used in the manufacturing processes of semiconductor devices that implement cooling expansion.

[0113] The cutting resistance R can be greater than 0 N / mm 2 And 40N / mm 2 The following can also be greater than 0 N / mm 2 And 35N / mm 2Below or 1~30N / mm 2 When the cutting resistance R is 40 N / mm 2 Under these conditions, the strength of the film adhesive will not become excessive, and it tends to achieve sufficient slitting ability. When the cutting resistance R is 20 N / mm... 2 When the above conditions are met, good stress propagation occurs during cooling expansion, which tends to result in better segmentation.

[0114] [Integrated membrane with grain cutting and bonding]

[0115] Figure 5 This is a schematic cross-sectional view illustrating one embodiment of a grain-jointed integral film. Figure 5 The die-cutting bonding integrated film 10 shown sequentially comprises a substrate layer 2, a pressure-sensitive adhesive layer 3, and an adhesive layer 1A formed from the aforementioned adhesive composition. The adhesive layer 1A can be formed from a film-like adhesive 1. The substrate layer 2 and the pressure-sensitive adhesive layer 3 can be dicing strips 4. When using such a die-cutting bonding integrated film 10, the semiconductor wafer lamination process is completed in one step, thus achieving operational efficiency. The die-cutting bonding integrated film can also be in the form of a film, sheet, strip, etc.

[0116] The cutting strip 4 has a substrate layer 2 and a pressure-sensitive adhesive layer 3 disposed on the substrate layer 2.

[0117] Examples of substrate layers 2 include polytetrafluoroethylene films, polyethylene terephthalate films, polyethylene films, polypropylene films, polymethylpentene films, polyimide films, and other plastic films. These substrate layers 2 can also undergo surface treatments such as primer coating, UV treatment, corona discharge treatment, grinding treatment, and etching treatment as needed.

[0118] The pressure-sensitive adhesive layer 3 is a layer formed of a pressure-sensitive adhesive. There are no particular limitations on the use of conventionally known pressure-sensitive adhesive layers in the wafer dicing field, provided that the pressure-sensitive adhesive has sufficient bonding force to prevent the semiconductor device from scattering during dicing and low bonding force to prevent damage to the semiconductor device during subsequent semiconductor device pick-up processes. The pressure-sensitive adhesive can also be either pressure-sensitive or radiation-cured. Pressure-sensitive adhesives exhibit constant adhesiveness under short-term pressure. On the other hand, radiation-cured adhesives are pressure-sensitive adhesives whose adhesiveness decreases upon irradiation with radiation (e.g., ultraviolet light).

[0119] From the perspective of economy and membrane operability, the thickness of the cutting strip 4 (substrate layer 2 and pressure-sensitive adhesive layer 3) can be 60-150 μm or 70-130 μm.

[0120] The integrated grain bonding film 10 can be obtained, for example, by preparing a film-like adhesive 1 and a cutting strip 4, and then bonding the film-like adhesive 1 to the pressure-sensitive adhesive layer 3 of the cutting strip 4. Furthermore, the integrated grain bonding film 10 can also be obtained, for example, by preparing the cutting strip 4 and, similarly to the method for forming the film-like adhesive 1, by coating the pressure-sensitive adhesive layer 3 of the cutting strip 4 with an adhesive composition (adhesive varnish).

[0121] When the film-like adhesive 1 is bonded to the pressure-sensitive adhesive layer 3 of the cutting strip 4, the integrated grain bonding film 10 can be formed by laminating the film-like adhesive 1 onto the cutting strip 4 under specific conditions (e.g., room temperature (20°C) or under heating) using a roller laminator, vacuum laminator, or the like. The integrated grain bonding film 10 can be manufactured continuously with excellent efficiency, and therefore can also be formed using a roller laminator under heating conditions.

[0122] Film-like adhesives and integrated films for bonding diced grains can be used in the manufacturing process of semiconductor devices, as well as in the manufacturing process of semiconductor devices composed of multiple stacked semiconductor elements.

[0123] Since film-like adhesives bond semiconductor elements to support components carrying semiconductor elements, they can also be preferably used as adhesives.

[0124] Furthermore, film adhesives can also be preferably used as adhesives for bonding semiconductor elements together in stacked MCPs (e.g., three-dimensional NAND memory), which are semiconductor devices composed of multiple stacked semiconductor elements.

[0125] Film adhesives can also be used, for example, as protective sheets to protect the back of semiconductor elements in flip-chip semiconductor devices, or as sealing sheets to seal the surface of semiconductor elements in flip-chip semiconductor devices and the bonded material.

[0126] Hereinafter, a semiconductor device manufactured using a film-type adhesive and a die-cutting bonding integrated film will be specifically described with reference to the accompanying drawings. Furthermore, various semiconductor device structures have been proposed in recent years, and the application of the film-type adhesive and die-cutting bonding integrated film of this embodiment is not limited to the semiconductor device with the structure described below.

[0127] [Semiconductor Devices]

[0128] Figure 6 This is a schematic cross-sectional view illustrating one embodiment of a semiconductor device. Figure 6The semiconductor device 100 shown includes a semiconductor element 11, a support member 12 for mounting the semiconductor element 11, and an adhesive member 15. The adhesive member 15 is disposed between the semiconductor element 11 and the support member 12, and adhesively bonds the semiconductor element 11 and the support member 12. The adhesive member 15 is a cured product of an adhesive composition (a cured product of a film adhesive). The connection terminals (not shown) of the semiconductor element 11 are electrically connected to external connection terminals (not shown) via wires 13 and are sealed by a sealing material 14.

[0129] Figure 7 This is a schematic cross-sectional view illustrating another embodiment of a semiconductor device. Figure 7 In the semiconductor device 110 shown, a first semiconductor element 11a is bonded to a support member 12 having terminals 16 via an adhesive member 15a (a cured adhesive composition (a cured film adhesive)). A second semiconductor element 11b is then bonded to the first semiconductor element 11a via an adhesive member 15b (a cured adhesive composition (a cured film adhesive)). The connection terminals (not shown) of the first and second semiconductor elements 11a and 11b are electrically connected to external connection terminals via wires 13 and sealed by a sealing material 14. Alternatively, Figure 7 The semiconductor device 110 shown is in Figure 6 The semiconductor device 100 shown also includes other semiconductor elements (11b) stacked on the surface of the semiconductor element (11a).

[0130] Figure 8 This is a schematic cross-sectional view illustrating another embodiment of a semiconductor device. Figure 8 The semiconductor device 120 shown includes a support member 12 and semiconductor elements 11a, 11b, 11c, and 11d stacked on the support member 12. For connection to connection terminals (not shown) formed on the surface of the support member 12, the four semiconductor elements 11a, 11b, 11c, and 11d are stacked at positions offset from each other in the lateral direction (orthogonal to the stacking direction) (see reference). Figure 8 Semiconductor element 11a is bonded to support element 12 via adhesive component 15a (cured adhesive composition (cured film adhesive)). Adhesive components 15b, 15c, and 15d (cured adhesive composition (cured film adhesive)) are also present between the three semiconductor elements 11b, 11c, and 11d, respectively. In other words, Figure 8 The semiconductor device 120 shown is in Figure 6 The semiconductor device 100 shown also includes other semiconductor elements (11b, 11c, 11d) stacked on the surface of the semiconductor element (11a).

[0131] The semiconductor device (package) has been described in detail above with respect to embodiments of the present invention, but the present invention is not limited to the above embodiments. For example, in Figure 8 The example shown illustrates a semiconductor device with four semiconductor elements stacked, but the number of stacked semiconductor elements is not limited to this. Furthermore, in... Figure 8 The example illustrates a semiconductor device in which semiconductor elements are stacked in a manner that is offset from each other in the lateral direction (a direction orthogonal to the stacking direction), but it is also possible for a semiconductor device in which semiconductor elements are stacked in a manner that is not offset from each other in the lateral direction (a direction orthogonal to the stacking direction).

[0132] [Semiconductor device manufacturing method]

[0133] Figure 6 , Figure 7 and Figure 8 The semiconductor device (semiconductor package) shown can be obtained by a method comprising: placing the aforementioned film adhesive between a semiconductor element and a support member, or between two semiconductor elements (first semiconductor element and second semiconductor element), and bonding the semiconductor element to the support member, or the semiconductor element (first semiconductor element) to the semiconductor element (second semiconductor element). More specifically, it can be obtained by heat-pressing and bonding the aforementioned film adhesive between the semiconductor element and the support member, or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element), and then, as needed, performing a wire bonding process, a sealing process based on a sealing material, a heat melting process including solder reflow, etc.

[0134] As a method of mediating a film adhesive between a semiconductor element and a support member, or between a semiconductor element (first semiconductor element) and a semiconductor element (second semiconductor element), as described below, it can be a method of attaching the semiconductor element with an adhesive sheet to the support member or the semiconductor element after the semiconductor element has been prefabricated.

[0135] Next, use Figure 5 One embodiment of the method for manufacturing a semiconductor device based on the die-cutting bonding monolithic film will be described. However, the method for manufacturing a semiconductor device based on the die-cutting bonding monolithic film is not limited to the method described below.

[0136] Semiconductor devices can be obtained, for example, by a method comprising: a process of attaching a semiconductor wafer to an adhesive layer of a die-bonding integral film (lamination process); a process of dicing the semiconductor wafer to which the adhesive layer is attached (dicing process); a process of fabricating a plurality of monolithic semiconductor elements with adhesive sheets by expanding a substrate layer under cooling conditions (cooling expansion process); a process of picking up the semiconductor elements with adhesive sheets from a pressure-sensitive adhesive layer (picking process); and a process of bonding the picked-up semiconductor elements with adhesive sheets to a support member via adhesive sheets (first bonding process). The method of manufacturing a semiconductor device may further include a process of bonding other semiconductor elements with adhesive sheets to the surface of a semiconductor element bonded to a support member via adhesive sheets (second bonding process).

[0137] The lamination process involves pressing a semiconductor wafer onto the adhesive layer 1A of the die-bonding integral film 10, bonding and holding it in place. This process can also be performed simultaneously using a pressing mechanism such as a pressing roller. Furthermore, the semiconductor wafer can be the same as described above.

[0138] Examples of semiconductor wafers include monocrystalline silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.

[0139] The dicing process is a process of dicing semiconductor wafers. Dicing can be performed, for example, from the circuit side of the semiconductor wafer using conventional methods. Furthermore, in this process, methods such as half-dicing (forming a half-groove on the semiconductor wafer) or laser-formed modified regions and then dicing (stealth laser dicing) can be used. Since the dicing of the adhesive layer of the die-bonded integral film exhibits excellent dicing properties based on cooling expansion, stealth laser dicing is preferred. There are no particular limitations on the dicing apparatus used in this process; conventionally known apparatus can be used.

[0140] The cooling expansion process is a process of expanding the substrate layer under cooling conditions. This allows for the production of multiple monolithic semiconductor devices with adhesive sheets. The expansion conditions under cooling can be arbitrarily set, for example, a cooling temperature of -30 to 5°C, a cooling time of 30 seconds to 5 minutes, a lifting amount of 5 to 20 mm, and a lifting speed of 50 to 300 mm / second.

[0141] Examples of semiconductor components (semiconductor chips) include ICs (integrated circuits). Examples of supporting components include lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resin and epoxy resin; modified plastic films made by impregnating and curing polyimide resin, epoxy resin, and other plastics in a substrate such as glass nonwoven fabric; and ceramics such as alumina.

[0142] The pick-up process is a process for peeling off semiconductor elements with adhesive sheets bonded to the die-cutting bonding monolithic film, separating the semiconductor elements with adhesive sheets from each other, and picking up the semiconductor elements with adhesive sheets. There is no particular limitation on the extension method for separating the semiconductor elements with adhesive sheets, and various conventionally known methods can be used. For example, a method for extending the substrate layer can be used to separate the semiconductor elements with adhesive sheets. Depending on the need, the extension can be performed under cooling conditions. There is no particular limitation on the pick-up method, and various conventionally known methods can be used. For example, a method can be used where each semiconductor element with adhesive sheets is lifted from the die-cutting bonding monolithic film side using a needle, and the lifted semiconductor elements with adhesive sheets are picked up by a pick-up device.

[0143] In this case, when the pressure-sensitive adhesive layer is radiation-cured (e.g., ultraviolet light), the pick-up process can be performed after the pressure-sensitive adhesive layer has been irradiated with radiation. This reduces the adhesive force between the pressure-sensitive adhesive layer and the adhesive sheet, making it easier to peel off the semiconductor device with the adhesive sheet. As a result, the pick-up process can be performed without damaging the semiconductor device with the adhesive sheet.

[0144] The first bonding process involves bonding the picked-up semiconductor element with adhesive sheet to the support member for mounting the semiconductor element using an adhesive sheet. Furthermore, if necessary, a second bonding process may also be included, in which other semiconductor elements with adhesive sheets are bonded to the surface of the semiconductor element bonded to the support member using an adhesive sheet. Bonding can be performed by compression. The compression conditions are not particularly limited and can be appropriately set as needed. Examples of compression conditions include a temperature of 80–160°C, a load of 5–15 N, and a time of 1–10 seconds. Additionally, the same support member as described above can be used as an example.

[0145] Depending on the requirements, the manufacturing method of a semiconductor device may also include a step of heat-curing an adhesive sheet. Through this bonding step, by heat-curing the adhesive sheet that bonds the semiconductor element to the support member, or to one semiconductor element (first semiconductor element) to another (second semiconductor element), a more secure bond can be achieved. During heat curing, pressure can also be applied simultaneously to cure it. The heating temperature in this step can be appropriately varied depending on the composition of the adhesive sheet. For example, the heating temperature can be 60–200°C. Furthermore, the temperature or pressure can be varied in stages.

[0146] The manufacturing method of a semiconductor device may also include, as needed, a process of electrically connecting the ends of the terminals (internal leads) of a support component to the electrode pads on the semiconductor element using bonding wires (wire bonding process). For example, gold wire, aluminum wire, or copper wire can be used as the bonding wire. The temperature for wire bonding (setting the bonding wire) can be in the range of 80–250°C or 80–220°C. The heating time can be from several seconds to several minutes. When setting the bonding wire, it can also be done under heating conditions within the above temperature range by using both ultrasonic vibration energy and pressure-based crimping energy.

[0147] The manufacturing method of a semiconductor device may also include, as needed, a process of sealing semiconductor elements with a sealing material (sealing process). This process is performed to protect the semiconductor elements or bonding wires mounted on a support member. This process can be performed by molding a sealing resin (sealing resin). For example, an epoxy resin can be used as the sealing resin. By embedding the support member and residue with heat and pressure during sealing, delamination caused by air bubbles in the bonding interface can be prevented.

[0148] The manufacturing method of a semiconductor device may also include, as needed, a step (post-curing step) to fully cure the sealing resin that was not adequately cured in the sealing process. Even if the adhesive sheet is not thermally cured in the sealing process, this step allows for simultaneous thermal curing of the adhesive sheet to bond and fix the device. The heating temperature in this step can be appropriately set depending on the type of sealing resin, for example, within the range of 165–185°C, and the heating time can be approximately 0.5–8 hours.

[0149] The manufacturing method of a semiconductor device may also include, as needed, a step of heating (heating and melting) the semiconductor element with an adhesive sheet bonded to a support member using a reflow oven. In this step, the resin-sealed semiconductor device may also be surface-mounted onto the support member. Examples of surface-mount methods include reflow soldering, where solder is pre-supplied onto a printed circuit board and then melted using warm air or similar methods. Examples of heating methods include hot air reflow soldering and infrared reflow soldering. Furthermore, the heating method can be applied to the entire device or to a specific area. The heating temperature can be, for example, in the range of 240–280°C.

[0150] Example

[0151] The present invention will now be specifically described with reference to embodiments, but the present invention is not limited thereto.

[0152] [Preparation of film-like adhesives]

[0153] (Examples 1-4 and Comparative Examples 1-3)

[0154] <Preparation of Adhesive Varnish>

[0155] Cyclohexanone was added to the mixture of components (A), (B), and (D) according to the ingredients and contents (unit: parts by mass) shown in Table 1, and the mixture was stirred. Component (C) was added to the mixture according to the ingredients and contents (unit: parts by mass) shown in Table 1 and stirred, followed by the addition of components (E) and (F), and stirred until all components became homogeneous, thus preparing the adhesive varnish. Note that the components shown in Table 1 refer to the following components, and the values ​​shown in Table 1 refer to the parts by mass of the solid components.

[0156] (A) Composition: Epoxy resin

[0157] (A1) Component: Epoxy resin with a fluorene backbone

[0158] (A1-1)PG-100 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd., an epoxy resin with a fluorene backbone, epoxy equivalent: 260 g / eq)

[0159] (A1-2)CG-500 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd., an epoxy resin with a fluorene backbone, epoxy equivalent: 310 g / eq)

[0160] (A2) Composition: Epoxy resin without a fluorene backbone

[0161] (A2-1)N-500P-10 (Trade name, manufactured by DIC Corporation, o-cresol phenolic varnish type epoxy resin, epoxy equivalent: 204g / eq)

[0162] (B) Component: Curing agent

[0163] (B-1)PSM-4326 (trade name, manufactured by Gunei Chemical Industry Co., Ltd., phenolic resin for varnish, hydroxyl equivalent: 105 g / eq, softening point: 118~122℃)

[0164] (B-2)GPH-103 (trade name, manufactured by NIPpon Kayaku Co., Ltd., biphenyl aryl phenolic resin, hydroxyl equivalent: 220~240g / eq, softening point: 99~106℃)

[0165] (B-3)MEH-7800M (Trade name, manufactured by Meiwa Plastic Industries, Ltd., phenolic resin for varnish, hydroxyl equivalent: 175g / eq, softening point: 78℃)

[0166] (C) Component: Elastomer

[0167] (C-1) Methyl ethyl ketone solution of acrylic rubber (acrylic rubber with a modified portion of the constituent units of SG-P3 (trade name, manufactured by Nagase ChemteX Corporation), weight average molecular weight: 800,000, Tg: 12℃)

[0168] (D) Composition: Inorganic filler

[0169] (D-1)YA050C (Trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size: 0.050μm)

[0170] (D-2)SC2050-HLG (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size: 0.50μm)

[0171] (E) Component: Coupling agent

[0172] (E-1)Y-9669 (trade name, manufactured by Momentive Performance Materials Japan LLC, 3-phenylaminopropyltrimethoxysilane)

[0173] (E-2)A-189 (trade name, manufactured by Nippon Unicar Company Limited, γ-mercaptopropyltrimethoxysilane)

[0174] (F) Ingredients: Curing accelerator

[0175] (F-1)2PZ-CN (trade name, manufactured by SHIKOKU CHEMICALS CORPORATION, 1-cyanoethyl-2-phenylimidazolium)

[0176] <Preparation of Film-like Adhesives>

[0177] The prepared adhesive varnish was filtered through a 100-mesh filter and then vacuum defoamed. A polyethylene terephthalate (PET) film with a thickness of 38 μm, which had undergone a demolding treatment, was prepared as a support membrane. The vacuum-defoamed adhesive varnish was coated onto the PET film. The coated adhesive varnish was dried at 90°C for 5 minutes, followed by drying at 130°C for 5 minutes, in two stages, to obtain the film-like adhesives (thickness: 10 μm) of Examples 1-4 and Comparative Examples 1-3 in stage B. In the film-like adhesive, the thickness was adjusted to 10 μm based on the amount of adhesive varnish applied.

[0178] [Segmentation Evaluation Based on Cooling Extension]

[0179] Adhesive sheets (5 mm wide × 100 mm long) were cut from the film adhesives of Examples 1-4 and Comparative Examples 1-3. The adhesive sheets were fixed to a pair of clamps (thick paper), and the portions of the adhesive sheets exposed from the clamps were removed. Thus, a sample (5 mm wide × 23 mm long) of the evaluation object was obtained. A cutting test was performed in a constant temperature bath (manufactured by AETEC Co., Ltd., TLF-R3-FW-PL-S) set at -15°C. That is, a cutting test was performed using an automatic stereographing instrument (manufactured by A&D Company, AZT-CA01, force sensor 50N) under compression mode, speed of 10 mm / min, and indentation distance of 5 mm, and the cutting work W, cutting strength P, and cutting elongation L at the time of film adhesive fracture were determined. Furthermore, the cutting coefficient m and cutting resistance R were calculated using the above equations (1) and (2). Furthermore, the cutting coefficient m and cutting resistance R are average values ​​obtained from performing more than 8 cutting tests on each embodiment and each comparative example. The cutting coefficient m tends to exhibit excellent segmentation performance based on cooling expansion as its value decreases. Cases with a cutting coefficient m of 60 or less are evaluated as "A" as cases with particularly excellent segmentation performance based on cooling expansion, cases with a cutting coefficient m of more than 60 but less than 70 are evaluated as "B", and cases with a cutting coefficient m of more than 70 are evaluated as "C". The results are shown in Table 1. In addition, the values ​​in parentheses in Table 1 represent the numerical values ​​of the cutting coefficient m.

[0180] To confirm the matching between the segmentation evaluation based on the cutting test and the segmentation evaluation based on actual cooling expansion, a grain-jointing integral film with the film adhesive of Example 3, Comparative Example 2 and Comparative Example 3 as the adhesive layer was prepared, and the segmentation of the adhesive layer (film adhesive) was evaluated under the following conditions.

[0181] • Silicon wafer thickness: 30μm

[0182] • Chip dimensions achieved through stealth laser cutting: 4mm x 12mm

[0183] • Cooling extension temperature: the same temperature as the constant temperature bath used in the cutting tests of the Examples and Comparative Examples.

[0184] • Lifting based on the expansion ring: 8mm

[0185] • Evaluation Criteria: Light was irradiated onto the silicon wafer after it was raised using an expansion ring. Chips where light passed through adjacent chips with adhesive layers (chips where the silicon wafer and adhesive layer were separated) were rated "A", while chips with areas where light did not pass through (chips where the silicon wafer and adhesive layer were not separated) were rated "B". The results are shown in Table 1.

[0186] As shown in Table 1, in the segmentation evaluation based on the cutting test, the film adhesives of Example 3 and Comparative Example 2, with a cutting coefficient m of 70 or less, were sufficient in the actual segmentation evaluation. In contrast, in the segmentation evaluation based on the cutting test, the film adhesive of Comparative Example 3, with a cutting coefficient m exceeding 70, was insufficient in the actual segmentation evaluation. Thus, it is confirmed that the segmentation evaluation based on the cutting test matches the actual segmentation based on cooling expansion.

[0187] [Adhesion Evaluation]

[0188] The film-like adhesives from Examples 1-4 and Comparative Examples 1-3 were cut into 5mm × 5mm pieces, and the PET film was peeled off to obtain a laminate containing the film-like adhesive sandwiched between two polyimide films (size: 1cm × 5cm, manufactured by UBE INDUSTRIES, LTD., UPILEX 50S). The laminate was then pressed together using a hot press machine (manufactured by TESTER SANGYO CO,. LTD.) at 120°C, 0.1MPa, and 5 seconds to obtain the measurement sample. One side of the polyimide film of the measurement sample was fixed to a 90° peel tester (manufactured by TESTER SANGYO CO,. LTD., TE-3001) using a Nystack (trade name, manufactured by NICHIBAN CO., LTD.), the worktable was heated to 120°C, and a peel test was performed to determine the peel strength.

[0189] The results are shown in Table 1.

[0190]

[0191] As shown in Table 1, the cutting coefficient m of the film adhesives of Examples 1-4, which contain epoxy resin with a fluorene backbone as a thermosetting resin, is 70 or less. Furthermore, the film adhesives of Examples 1-4 exhibit superior peel strength compared to the film adhesives of Comparative Examples 1-3, which do not contain epoxy resin with a fluorene backbone as a thermosetting resin. These results confirm that the film adhesive of the present invention exhibits excellent segmentation based on cooling expansion and excellent adhesion to semiconductor wafers.

[0192] Symbol Explanation

[0193] 1-Film adhesive, 1A-Adhesive layer, 2-Substrate layer, 3-Pressure-sensitive adhesive layer, 4-Cut strip, 10-Cut die bonding integrated film, 11, 11a, 11b, 11c, 11d-Semiconductor element, 12-Support component, 13-Wire, 14-Sealing material, 15, 15a, 15b, 15c, 15d-Adhesive component, 16-Terminal, 20-Sample fixing fixture, 20a-Opening, 21-Press-in fixture, 21a-Tip, 100, 110, 120-Semiconductor device.

Claims

1. A grain-jointing integrated film, comprising sequentially a substrate layer, a pressure-sensitive adhesive layer, and an adhesive layer formed of a thermosetting film-like adhesive. The film-like adhesive contains epoxy resin, phenolic resin, acrylic rubber, and silica filler. The epoxy resin contains an epoxy resin with a fluorene backbone.

2. A semiconductor device comprising: Semiconductor components; Support component, which mounts the semiconductor element; and An adhesive component is disposed between the semiconductor element and the support component to bond the semiconductor element and the support component. The adhesive component is a cured product of a thermosetting film adhesive. The film-like adhesive contains epoxy resin, phenolic resin, acrylic rubber, and silica filler. The epoxy resin contains an epoxy resin with a fluorene backbone.

3. The semiconductor device according to claim 2, further comprising other semiconductor elements stacked on the surface of the semiconductor element.

4. A method for manufacturing a semiconductor device, comprising: The process of bonding the semiconductor element to the support component, or the first semiconductor element to the second semiconductor element, by intermediating a thermosetting film adhesive between a semiconductor element and a support component, or between a first semiconductor element and a second semiconductor element. The film-like adhesive contains epoxy resin, phenolic resin, acrylic rubber, and silica filler. The epoxy resin contains an epoxy resin with a fluorene backbone.

5. A method for manufacturing a semiconductor device, comprising: The process of attaching the adhesive layer of the die-cutting bonding integral film according to claim 1 onto a semiconductor wafer; The process of cutting the semiconductor wafer to which the adhesive layer is attached; The process of fabricating multiple monolithic semiconductor devices with adhesive sheets by expanding the substrate layer under cooling conditions; The process of picking up the semiconductor element with the adhesive sheet from the pressure-sensitive adhesive layer; and The process of bonding the picked-up semiconductor element with adhesive sheet to the support member by means of adhesive sheet.

6. The method for manufacturing a semiconductor device according to claim 5, further comprising: The process of bonding other semiconductor elements with adhesive sheets to the surface of the semiconductor element bonded to the support member by means of adhesive sheets.

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