Film-shaped adhesive, adhesive composition, dicing die attach film, and semiconductor package and method for manufacturing semiconductor package

Abstract

A film-shaped adhesive, an adhesive composition, a dicing die attach film, and a semiconductor package and a method for manufacturing the same, the film-shaped adhesive containing an epoxy resin (A), an epoxy resin curing agent (B), and a high molecular component (C), wherein the high molecular component (C) is an addition polymer or a ring-opening polymer obtained by a chain reaction and has a cyclodextrin structure and an adamantyl group in a side chain.

Description

Technical Field

[0001] This invention relates to film adhesives, adhesive compositions, chip dicing and mounting films, and semiconductor packaging and methods for manufacturing semiconductor packaging. Background Technology

[0002] In recent years, stacked MCPs (Multi-Chip Packages), which consist of multiple layers of semiconductor chips, have become increasingly popular, and are used in memory packages for mobile phones and portable audio devices. Furthermore, with the increasing multifunctionality of mobile phones and other devices, the density and integration of packaging are constantly advancing. Alongside this, the multi-layering of semiconductor chips is developing.

[0003] In the manufacturing process of such memory packages, thermosetting film adhesives (chip mounting films, chip bonding films) are used for bonding the wiring substrate to the semiconductor chip and for bonding the semiconductor chips together. As chips are stacked in multiple layers, the chip mounting film needs to be formed into a thinner shape. Furthermore, with the miniaturization of wafer wiring patterns, heat is easily generated on the surface of semiconductor components. Therefore, to dissipate heat to the outside of the package, thermally conductive fillers are mixed into the chip mounting film to achieve high thermal conductivity.

[0004] As a material for thermosetting film adhesives intended for use in so-called chip mounting films, compositions are known, for example, of a combination of a curable resin with a weight-average molecular weight of less than 10,000, a curing agent, and nepheline (e.g., Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-24963 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Semiconductor packages consist of components made of various materials, including substrates (semiconductors, glass), lead frames (metal), circuitry, adhesive layers, and encapsulation layers. Therefore, due to the different coefficients of thermal expansion of these components, warping can sometimes occur in semiconductor packages. This trend intensifies with the miniaturization and thinning of semiconductor packages. Furthermore, in multilayer packages with many layers, the impact of warping is greater compared to single-layer semiconductor packages. If warping occurs in a semiconductor package, it can lead to various problems during assembly and use, such as poor connection between external terminals and the mounting substrate, cracks in the internal structure, and wire breakage.

[0010] In semiconductor packaging materials, resin-containing materials have a relatively large coefficient of thermal expansion compared to metal materials, leading to various studies aimed at reducing thermal expansion. For example, Patent Document 1 addresses the problems associated with using inorganic fillers as a means of reducing thermal expansion, describing a composition that reduces the coefficient of thermal expansion by using a curable resin with a specific weight-average molecular weight, a curing agent, and nepheline as a filler. However, the composition described in Patent Document 1 has manufacturing limitations in terms of using a special inorganic filler.

[0011] On the other hand, when resin-containing materials are used as adhesives or encapsulants, sufficient adhesion to the adhered objects is required. Previously, it was known that the adhesive strength decreased by including inorganic fillers, and it was difficult to achieve both reduced warpage and excellent adhesive strength using methods that utilize inorganic fillers.

[0012] The present invention aims to provide a film-like adhesive that effectively suppresses warping and exhibits excellent adhesion to the substrate, and an adhesive composition suitable for preparing the film-like adhesive. Furthermore, the present invention aims to provide a die-cutting chip mounting film and a semiconductor package using the above-described film-like adhesive, as well as a method for manufacturing the semiconductor package.

[0013] Methods for solving problems

[0014] In view of the above-mentioned problems, the inventors have conducted in-depth research and found that the above-mentioned problems can be solved by using a polymer component containing both cyclodextrin structure and adamantyl group in the side chain of the film adhesive containing epoxy resin, epoxy resin curing agent and polymer components.

[0015] This invention was completed based on further repeated research based on the above insights.

[0016] The above-mentioned problems of the present invention are solved by the following means. [1]

[0018] A film-like adhesive comprising epoxy resin (A), epoxy resin curing agent (B), and polymer component (C), wherein, The polymeric component (C) is an addition polymer or ring-opening polymer obtained through a chain reaction, and has a cyclodextrin structure and adamantyl group in its side chain. [2]

[0020] According to the film adhesive described in [1], the content of the polymer component (C) in the total solids of the film adhesive is 15% to 90% by mass. [3]

[0022] According to the film adhesive described in [1] or [2], the component having a cyclodextrin structure accounts for 20 mol% to 80 mol% of the total components of the polymer component (C), and the component having an adamantyl group accounts for 20 mol% to 80 mol% of the total components of the polymer component (C). [4]

[0024] The film adhesive according to any one of [1] to [3], wherein the polymer component (C) is an addition polymer formed by chain polymerization of (meth)acryloyl groups or an open-ring polymer formed by chain polymerization of epoxy groups. [5]

[0026] The film adhesive according to any one of [1] to [4], wherein the epoxy resin (A) comprises a dicyclopentadiene type epoxy resin. [6]

[0028] The film adhesive according to any one of [1] to [5] contains an inorganic filler (D). [7]

[0030] The film adhesive according to any one of [1] to [6], wherein the storage modulus of the cured product formed by curing the film adhesive is 0.1 GPa to 1.0 GPa. [8]

[0032] The film adhesive according to any one of [1] to [7], wherein the tanδ of the cured product formed by curing the film adhesive is 0.2 to 1.2. [9]

[0034] The film adhesive according to any one of [1] to [8], wherein the coefficient of linear expansion α1 of the cured product formed by curing the film adhesive is 10ppm / ℃ to 50ppm / ℃.

[10]

[0036] The film adhesive according to any one of [1] to [8], wherein the linear expansion coefficient α1 of the cured product is 10ppm / ℃ to 50ppm / ℃, and the linear expansion coefficient α2 is 80ppm / ℃ to 200ppm / ℃.

[11]

[0038] The film adhesive according to any one of [1] to

[10] , wherein the thickness of the film adhesive is 1 μm to 100 μm.

[12]

[0040] An adhesive composition comprising an epoxy resin (A), an epoxy resin curing agent (B), and a polymer component (C), wherein, The polymeric component (C) is an addition polymer or ring-opening polymer obtained through a chain reaction, and has a cyclodextrin structure and adamantyl group in its side chain.

[13]

[0042] A chip dicing and mounting film is formed by laminating a film-like adhesive as described in any one of [1] to

[11] with a dicing film.

[14]

[0044] A method for manufacturing a semiconductor package, comprising: In the first process, an adhesive layer is provided by hot-pressing the film adhesive described in any one of [1] to

[11] onto the back side of a semiconductor wafer on which a semiconductor circuit is formed on the surface, and a cutting film is provided in between the adhesive layer; In the second step, the semiconductor wafer and the adhesive layer are integrally cut to obtain a semiconductor chip with an adhesive layer having a film-like adhesive sheet and a semiconductor chip on the cut film. In the third step, the semiconductor chip with the adhesive layer is peeled off from the dicing film, and the semiconductor chip with the adhesive layer is thermally bonded to the wiring substrate through the adhesive layer; and The fourth step involves heat curing the adhesive layer.

[15]

[0046] A wire-bonded semiconductor package comprising a thermosetting material of the film adhesive described in any one of [1] to

[11] .

[0047] In this invention, the numerical range represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit.

[0048] Invention Effects

[0049] The film-like adhesive of the present invention can suppress warping and exhibits excellent adhesion to the adherend. The adhesive composition of the present invention is suitable for obtaining the above-mentioned film-like adhesive.

[0050] The semiconductor package manufacturing method according to the present invention can produce a semiconductor package that is not prone to warping and has excellent bonding reliability. Attached Figure Description

[0051] Figure 1 This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of the first step of the semiconductor package manufacturing method of the present invention.

[0052] Figure 2This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of the second step of the semiconductor package manufacturing method of the present invention.

[0053] Figure 3 This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of the third step of the semiconductor package manufacturing method of the present invention.

[0054] Figure 4 This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of the process for connecting bonding leads in the semiconductor package manufacturing method of the present invention.

[0055] Figure 5 This is a schematic longitudinal cross-sectional view illustrating an example of a multilayer stacked embodiment of the semiconductor package manufacturing method of the present invention.

[0056] Figure 6 This is a schematic longitudinal cross-sectional view illustrating other multilayer stacked embodiments of the semiconductor package manufacturing method of the present invention.

[0057] Figure 7 This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of a semiconductor package manufactured by the semiconductor package manufacturing method of the present invention.

[0058] Figure 8 (A) is an illustrative diagram schematically showing a preferred example of the structure of the polymer component (C). Figure 8 (B) is an illustrative diagram schematically showing the interactions of the side chains of the polymer component (C).

[0059] Figure 9 This is an explanatory diagram showing the relationship between the inflection point and the linear expansion coefficients α1 and α2 in the measurement curve obtained from the thermomechanical analysis (TMA) of the cured film adhesive. Detailed Implementation

[0060] [Film adhesive]

[0061] The film-like adhesive of the present invention comprises epoxy resin (A), epoxy resin curing agent (B), and polymer component (C). The polymer component (C) is a polymer having a cyclodextrin structure and an adamantyl group in its side chains, respectively, and the polymerization morphology of this polymer is addition polymerization or ring-opening polymerization based on a chain reaction. That is, the polymer component (C) is a polymer that is an addition polymer or a ring-opening polymer formed by a chain reaction, and has both a cyclodextrin structure and an adamantyl group in its side chains.

[0062] In this invention, "film" refers to a thin film with a thickness of less than 200 μm. There are no particular limitations on shape, size, etc., and they can be adjusted appropriately according to the intended use.

[0063] The film adhesive of the present invention is in the pre-curing state, i.e., the B-stage state.

[0064] The film adhesive of the present invention is less prone to warping in the laminate with the adherend and has excellent adhesion to the adherend.

[0065] The film-like adhesive of the present invention can be used as a chip mounting film in semiconductor manufacturing processes.

[0066] The following is a more detailed explanation of film adhesives.

[0067] <Epoxy Resin (A)>

[0068] The epoxy resin (A) described above can be used without particular restriction as long as it is a thermosetting resin with epoxy groups, and can be any of liquid, solid, or semi-solid. In this invention, liquid refers to a softening point of less than 25°C, solid refers to a softening point of 60°C or higher, and semi-solid refers to a softening point between the softening points of the liquid and solid mentioned above (25°C or higher and less than 60°C). As for the epoxy resin (A) used in this invention, from the viewpoint of obtaining a film adhesive that can achieve a low melt viscosity within a suitable temperature range (e.g., 60–120°C), a softening point of 100°C or lower is preferred. It should be noted that in this invention, the softening point refers to the value determined by the softening point test (ring and ball method) (test conditions: according to JIS-K7234:1986).

[0069] The epoxy equivalent of epoxy resin (A) is preferably 500 g / eq or less, more preferably 150 to 450 g / eq. It should be noted that, in this invention, epoxy equivalent refers to the number of grams (g / eq) of resin containing 1 gram equivalent of epoxy groups.

[0070] The weight-average molecular weight of epoxy resin (A) is generally preferably less than 10,000, more preferably less than 5,000. There is no particular limitation on the lower limit, but in practice it is above 300.

[0071] The weight-average molecular weight is based on GPC (Gel Permeation Chromatography) analysis. (Unless otherwise specified, the same applies to other resins.)

[0072] Examples of epoxy resin (A) skeletons include phenolic resin clear varnish type, o-cresol phenolic resin clear varnish type, cresol phenolic resin clear varnish type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthol type, triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD ​​type, bisphenol S type, and tris(hydroxymethylmethane) type.

[0073] The epoxy resin (A) preferably has a fused ring structure in its molecule. The number of rings constituting this fused ring structure is preferably 2 to 7, more preferably 2 to 5, further preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. Furthermore, each ring constituting the fused ring structure may have a cross-linked structure. The number of rings constituting the fused ring structure is preferably a 5-membered ring and / or a 6-membered ring (for example, dicyclopentadiene has a fused ring structure of 5-membered and 6-membered rings, with the 6-membered ring having a cross-linked structure).

[0074] Examples of fused-ring structures that can be used in epoxy resin (A) include dicyclopentadiene, fluorene (preferably fluorene-bisphenol), and naphthalene (preferably including naphthol or naphthalenediol). Among these, dicyclopentadiene structures (dicyclopentadiene-type epoxy resins) and naphthalene structures (naphthalene-type epoxy resins) are preferred. That is, epoxy resin (A) preferably includes dicyclopentadiene-type epoxy resins and / or naphthalene-type epoxy resins, and more preferably dicyclopentadiene-type epoxy resins.

[0075] In the solid components (specifically, components other than solvents) of the film adhesive of the present invention (100% by mass), the content of epoxy resin (A) is preferably 8 to 80% by mass, more preferably 8 to 70% by mass.

[0076] When the film adhesive of the present invention does not contain inorganic filler (D), the content of epoxy resin (A) in the above-mentioned solid component is more preferably 23-70% by mass, more preferably 35-70% by mass, more preferably 45-70% by mass, and more preferably 55-70% by mass. Furthermore, when the film adhesive of the present invention contains inorganic filler (D), the content of epoxy resin (A) in the above-mentioned solid component may be 10-60% by mass, or 20-50% by mass, or 20-40% by mass.

[0077] The proportion of epoxy resin (A) in the total content (100% by mass) of epoxy resin (A) and polymer component (C) is preferably 20-75% by mass, more preferably 25-75% by mass, even more preferably 30-70% by mass, and even more preferably 35-60% by mass.

[0078] <Epoxy Resin Curing Agent (B)>

[0079] As the epoxy resin curing agent (B) mentioned above, any curing agent such as amines, acid anhydrides, or polyphenols can be used. In this invention, from the perspective of producing a film adhesive with high storage stability that has low melt viscosity, exhibits curability at high temperatures exceeding a certain temperature, has rapid curing properties, and can be stored at room temperature for a long time, a latent curing agent is preferred.

[0080] Examples of potential curing agents include dicyandiamide compounds, imidazole compounds, curing catalyst complexes of polyphenolic compounds, hydrazide compounds, boron trifluoride-amine complexes, amine imide compounds, polyamine salts, and their modified forms, as well as microencapsulated substances. They can be used alone or in combination of two or more. Imidazole compounds are preferred due to their superior potential (excellent stability at room temperature and the property of curing upon heating) and faster curing speed.

[0081] The content of epoxy resin curing agent (B) in the adhesive composition can be appropriately set according to the type and reaction mode of the curing agent. For example, relative to 100 parts by weight of epoxy resin (A), it can be set to 0.5 to 100 parts by weight, 1 to 80 parts by weight, 2 to 50 parts by weight, and preferably 4 to 20 parts by weight. In addition, when using an imidazole compound as epoxy resin curing agent (B), relative to 100 parts by weight of epoxy resin (A), it is preferable to set the imidazole compound to 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, even more preferably 1.5 to 6 parts by weight, and even more preferably 2 to 4 parts by weight.

[0082] <Polymer Component (C)>

[0083] The polymer component (C) is a polymer in which, within one molecule, the side chains contain a cyclodextrin structure (a monovalent group obtained by removing one hydrogen atom from cyclodextrin) and an adamantyl group (a monovalent group obtained by removing one hydrogen atom from adamantane). That is, the polymer component (C) has a chemical structure different from the so-called rotaxane structure. It is believed that the cyclodextrin structure of the polymer compound (C) functions as the host group, while the adamantyl group functions as the guest group; through host-guest interaction, this contributes to improved adhesive strength.

[0084] Figure 8 (A) shows a preferred example of the structure of the polymeric component (C). The polymeric component (C) has a main chain 10 in its molecule, and has four cyclodextrin structures 11 and four adamantyl groups 12 as side chains. Figure 8 (B) shows a polymeric component (C) consisting of two molecules, where the upper molecule has two cyclodextrin structures 11 that capture the two adamantyl groups 12 of the lower molecule (the cyclodextrin structure captures the adamantyl group), and the lower molecule has one cyclodextrin structure 11 that captures the one adamantyl group 12 of the upper molecule.

[0085] The polymeric component (C) is an addition polymer or a ring-opening polymer obtained through a chain reaction, wherein its main chain is formed through a chain reaction. In this invention, "an addition polymer or a ring-opening polymer obtained through a chain reaction" means that the polymeric component (C) has a structure obtained through a chain reaction, and does not imply a limitation on its preparation method. When the polymeric component (C) is an addition polymer, it can be a polymer obtained by chain polymerization of groups having carbon-carbon double bonds, such as vinyl, vinyl ether, vinyl sulfide, styrene, (meth)acryloyl, and their derivatives. When the polymeric component (C) is a ring-opening polymer, it can be a polymer obtained by chain polymerization of cyclic ether groups such as epoxy, oxobutyl, etc. Preferably, the polymeric component (C) is an addition polymer obtained by chain polymerization of (meth)acryloyl groups or a ring-opening polymer obtained by chain polymerization of epoxy groups.

[0086] The cyclodextrin structure is preferably derived from α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin. The cyclodextrin structure is preferably an unsubstituted cyclodextrin structure.

[0087] The adamantyl group is preferably an unsubstituted adamantyl group.

[0088] The cyclodextrin structure and adamantyl group can be introduced into the side chain of the polymer component (C) via linking groups.

[0089] The polymeric component (C) can be referred to as a polymer containing a component having a cyclodextrin structure (repeating unit) and a component having an adamantyl group. The polymeric component (C) may also contain components other than those having a cyclodextrin structure and components other than those having an adamantyl group (hereinafter referred to as "other components").

[0090] The constituents with cyclodextrin structures are usually different from those with adamantyl groups.

[0091] The proportion of the component with the cyclodextrin structure in all the components of the polymer component (C) (hereinafter also referred to as the cyclodextrin modification rate) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%.

[0092] The proportion of the adamantyl group in the total composition of the polymer (C) (hereinafter also referred to as the adamantyl modification rate) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%.

[0093] When the polymer component (C) contains other constituent components, the proportion of the other constituent components in the total constituent components of the polymer component (C) is preferably 20 mol% or less, more preferably 10 mol% or less.

[0094] In the polymer component (C), the molar ratio (B / A) of the content (B) of the constituent component having an adamantyl group to the content (A) of the constituent component having a cyclodextrin structure is preferably 0.25 to 4.00, more preferably 0.40 to 2.50, even more preferably 0.50 to 2.00, even more preferably 0.55 to 1.80, and even more preferably 0.60 to 1.50.

[0095] There is no particular limitation on the weight-average molecular weight of the polymer component (C), but it is preferably 1,000 or more, more preferably 1,000 to 1,000,000, and even more preferably 10,000 to 1,000,000.

[0096] There are no particular limitations on the glass transition temperature (Tg) of the polymer component (C), but it is preferably above 0°C, more preferably 20 to 100°C, and even more preferably 20 to 60°C.

[0097] The Tg of the aforementioned polymer component (C) is the peak temperature of tanδ in the dynamic viscoelasticity measurement. Specifically, Tg can be determined as follows.

[0098] A solution containing dissolved polymer (C) was coated onto a release film and heated to dry, forming a polymer film on the release film. The release film was then peeled off and removed. The polymer film was measured using a dynamic viscoelasticity measuring device (trade name: Rheogel-E4000F, UBM) under conditions of a temperature range of 20–300 °C, a heating rate of 5 °C / min, and a frequency of 1 Hz. The obtained tanδ peak temperature (the temperature at which tanδ shows its maximum) was taken as Tg.

[0099] The polymer component (C) can be synthesized or commercially available products can be used.

[0100] In the case of synthesis, the synthesis method is not particularly limited. For example, it can be a method of introducing the cyclodextrin structure and the adamantyl group via their reactive groups in a polymer having reactive groups for introducing the cyclodextrin structure and reactive groups for introducing the adamantyl group, or it can be a method of polymerizing monomers having the cyclodextrin structure and monomers having the adamantyl group as raw materials.

[0101] In the total solids content (100% by mass) of the film adhesive, the content of polymeric component (C) is preferably 15-90% by mass, more preferably 25-90% by mass.

[0102] When the film adhesive of the present invention does not contain inorganic filler (D), the content of polymeric component (C) in the above-mentioned solid component is more preferably 25-75% by mass, more preferably 25-60% by mass, more preferably 25-50% by mass, and more preferably 25-40% by mass. Furthermore, when the film adhesive of the present invention contains inorganic filler (D), the content of polymeric component (C) in the above-mentioned solid component can be 15-60% by mass, or 20-50% by mass, or 20-40% by mass.

[0103] The proportion of polymer component (C) in the total content (100% by mass) of epoxy resin (A) and polymer component (C) is preferably 25-80% by mass, more preferably 25-75% by mass, even more preferably 30-70% by mass, and even more preferably 40-65% by mass.

[0104] <Inorganic Filler (D)>

[0105] Inorganic fillers (D) can use inorganic filler materials commonly used in adhesive compositions without particular restrictions.

[0106] Examples of inorganic fillers (D) include: ceramics such as silicon dioxide, clay, gypsum, calcium carbonate, barium sulfate, alumina (alumina trioxide), beryllium oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride, and boron nitride; metals or alloys such as aluminum, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, and solder; carbon-based materials such as carbon nanotubes, carbon nanofibers, and graphene; and various inorganic powders.

[0107] The particle size (d50) of the inorganic filler (D) is not particularly limited, but from the perspective of thinning the film adhesive, it is preferably 0.01 μm to 6.0 μm, more preferably 0.01 μm to 5.0 μm, more preferably 0.1 μm to 3.5 μm, and even more preferably 0.1 μm to 1.0 μm. In this invention, the particle size (d50) refers to the so-called median particle size, which is the particle size that reaches 50% cumulative distribution when the total volume of the particles is set to 100%, as determined by laser diffraction and scattering.

[0108] The Mohs hardness of inorganic filler materials is not particularly limited, but is preferably 2 or higher, and more preferably 2 to 9. Mohs hardness can be measured using a Mohs hardness tester.

[0109] The aforementioned inorganic filler (D) may contain an inorganic filler material with thermal conductivity (an inorganic filler material with a thermal conductivity of 12 W / m·K or higher) or an inorganic filler material without thermal conductivity (an inorganic filler material with a thermal conductivity of less than 12 W / m·K).

[0110] The thermally conductive inorganic filler (D) is a particle composed of a thermally conductive material or a particle whose surface is covered with a thermally conductive material. The thermal conductivity of these thermally conductive materials is preferably 12 W / m·K or more, and more preferably 30 W / m·K or more.

[0111] If the thermal conductivity of the aforementioned thermally conductive material is above the preferred lower limit value, the amount of inorganic filler (D) mixed to obtain the target thermal conductivity can be reduced, the increase in the melt viscosity of the chip mounting film can be suppressed, and the embedding performance of the substrate's uneven parts during lamination can be further improved. As a result, the generation of voids can be suppressed more reliably.

[0112] In this invention, the thermal conductivity of the aforementioned thermally conductive material refers to the thermal conductivity at 25°C, and the literature values ​​for each material can be used. In cases where no literature record exists, for example, if the thermally conductive material is ceramic, the value measured according to JIS R 1611:2010 can be used; if the thermally conductive material is metal, the value measured according to JIS H 7801:2005 can be used.

[0113] Examples of thermally conductive inorganic fillers (D) include, for example, thermally conductive ceramics, with alumina particles (thermal conductivity: 36 W / m·K), aluminum nitride particles (thermal conductivity: 150 W / m·K to 290 W / m·K), boron nitride particles (thermal conductivity: 60 W / m·K), zinc oxide particles (thermal conductivity: 54 W / m·K), silicon nitride particles (thermal conductivity: 27 W / m·K), silicon carbide particles (thermal conductivity: 200 W / m·K), and magnesium oxide particles (thermal conductivity: 59 W / m·K) being preferred.

[0114] In particular, alumina particles are preferred from the perspectives of high thermal conductivity, dispersibility, and ease of acquisition. Furthermore, aluminum nitride particles and boron nitride particles have higher thermal conductivity than alumina particles, and are therefore preferred from this perspective. In this invention, alumina particles and aluminum nitride particles are preferred.

[0115] In addition, as an inorganic filler (D) with thermal conductivity, examples include metal particles with higher thermal conductivity than ceramics, or particles with a metal coating on their surface. For example, single metal fillers such as silver (thermal conductivity: 429 W / m·K), nickel (thermal conductivity: 91 W / m·K), and gold (thermal conductivity: 329 W / m·K), as well as polymer particles such as acrylic or silicone resins with these metals coated on their surface, are preferred.

[0116] In this invention, silicon dioxide is preferably used as the inorganic filler (D).

[0117] The inorganic filler (D) may be surface treated or surface modified. Examples of surface treatment agents used in such surface treatment or surface modification include silane coupling agents, phosphoric acid or phosphoric acid compounds, and surfactants. In addition to the matters described in this specification, for example, the silane coupling agents, phosphoric acid or phosphoric acid compounds and surfactants described in the section on thermally conductive fillers in International Publication No. 2018 / 203527 or the section on aluminum nitride fillers in International Publication No. 2017 / 158994 may also be used.

[0118] As a method for blending inorganic filler (D) into resin components such as epoxy resin (A), epoxy resin curing agent (B), and polymer component (C), the following methods can be used: a method of directly blending powdered inorganic filler with a silane coupling agent, phosphoric acid or phosphoric acid compound, and surfactant as needed (integral blending method); or a method of dispersing inorganic filler treated with a silane coupling agent, phosphoric acid or phosphoric acid compound, or surfactant in an organic solvent and blending to obtain a slurry-like inorganic filler.

[0119] Furthermore, there are no particular limitations on the method of treating inorganic filler (D) with silane coupling agent, and examples include: a wet method in which inorganic filler (D) and silane coupling agent are mixed in a solvent; a dry method in which inorganic filler (D) and silane coupling agent are mixed in the gas phase; the above-mentioned integral blending method; etc.

[0120] In particular, while aluminum nitride particles contribute to high thermal conductivity, they are prone to hydrolysis, generating ammonium ions. Therefore, it is preferable to use them in combination with phenolic resins with low moisture absorption, or to inhibit hydrolysis through surface modification. As a method for surface modification of aluminum nitride, the following methods are particularly preferred: providing an aluminum oxide layer on the surface to improve water resistance, and performing surface treatment with phosphoric acid or a phosphoric acid compound to improve affinity with the resin.

[0121] Silane coupling agents are compounds with at least one hydrolyzable group such as an alkoxy or aryloxy bonded to a silicon atom. Alternatively, alkyl, alkenyl, or aryl groups may be bonded. The alkyl group is preferably an alkyl group substituted with an amino, alkoxy, epoxy, or (meth)acryloyloxy group, and more preferably an alkyl group substituted with an amino (preferably phenylamino), alkoxy (preferably epoxypropoxy), or (meth)acryloyloxy group.

[0122] Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and so on.

[0123] The silane coupling agent and surfactant preferably contain 0.1 to 25.0 parts by weight relative to 100 parts by weight of the inorganic filler (D), more preferably 0.1 to 10.0 parts by weight, and even more preferably 0.1 to 2.0 parts by weight.

[0124] By setting the contents of the silane coupling agent and surfactant within the aforementioned preferred range, the aggregation of the inorganic filler (D) can be suppressed, and the peeling at the bonding interface caused by the volatilization of excessive silane coupling agent and surfactant during semiconductor assembly heating processes (e.g., reflow processes) can be suppressed, thereby inhibiting the formation of voids.

[0125] Inorganic fillers (D) can take the form of flakes, needles, filaments, spheres, or scales. From the perspective of high filling capacity and flowability, spherical particles are preferred.

[0126] The content of inorganic filler (D) in the total solids component (100% by mass) of the film adhesive is preferably 50% by mass or less, more preferably 45% by mass or less.

[0127] When the film adhesive of the present invention contains inorganic filler (D), the content of inorganic filler (D) is preferably 10 to 50% by mass of the total solids content (100% by mass) of the film adhesive, more preferably 20 to 45% by mass.

[0128] When the film adhesive of the present invention contains inorganic filler (D), the content of inorganic filler (D) is preferably 80 parts by mass or less relative to the total content of epoxy resin (A) and polymer component (C) of 100 parts by mass. When it is within the above range, the adhesive strength will not be significantly reduced even if inorganic filler (D) is contained.

[0129] When the film adhesive of the present invention contains inorganic filler (D), the content of inorganic filler (D) is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, relative to the total content of epoxy resin (A) and polymer component (C) of 100 parts by mass.

[0130] <Other Ingredients>

[0131] In addition to epoxy resin (A), epoxy resin curing agent (B), polymer component (C), and inorganic filler (D), the film adhesive of the present invention may also contain ion scavengers, curing catalysts, viscosity modifiers, antioxidants, flame retardants, colorants, etc., without impairing the effects of the present invention. For example, it may contain other additives as disclosed in International Publication No. 2017 / 158994.

[0132] <Thickness of film adhesive>

[0133] The thickness of the film adhesive is preferably 1 to 100 μm, more preferably 1 to 80 μm, even more preferably 1 to 50 μm, and even more preferably 1 to 20 μm.

[0134] The thickness of the film adhesive can be measured using a contact / linear measuring instrument (desktop contact thickness measuring device).

[0135] Properties of film adhesives

[0136] In this invention, the cured product formed by curing the film adhesive of this invention (also referred to as "the cured product of the film adhesive of this invention") refers to a substance in which epoxy resin (A) is in a thermosetting state (thermosetting product).

[0137] In this invention, "cured product of film adhesive" refers to the cured product of film adhesive that has been cured by treating it at 180°C for 1 hour.

[0138] The storage modulus of the cured film adhesive of the present invention at 25°C is preferably 0.1–1.2 GPa, more preferably 0.2–1.0 GPa, even more preferably 0.2–0.8 GPa, even more preferably 0.2–0.6 GPa, and even more preferably 0.2–0.4 GPa. A lower storage modulus tends to suppress warping.

[0139] The storage modulus of the cured film adhesive can be measured using a dynamic viscoelasticity measuring device, specifically, by the method described in the examples.

[0140] The loss tangent (tanδ) of the cured film adhesive of the present invention at 25°C is preferably 0.2 to 1.2, more preferably 0.3 to 1.2, and even more preferably 0.5 to 1.0. By keeping tanδ within the above-preferred range, there is a tendency to improve adhesive strength.

[0141] The tanδ of the cured film adhesive can be measured using a dynamic viscoelasticity measuring device, specifically, by the method described in the examples.

[0142] The cured film adhesive of the present invention preferably exhibits two different coefficients of linear expansion in the temperature region before and after the inflection point in the measurement curve (vertical axis: change (μm), horizontal axis: temperature (°C)) obtained by thermomechanical analysis (TMA) of the coefficient of linear expansion. The coefficient of linear expansion in the temperature region closer to the inflection point is designated as α1, and the coefficient of linear expansion in the temperature region closer to the inflection point is designated as α2. Figure 9 The two linear expansion coefficients α1 and α2 in the measurement curve obtained in the TMA measurement are illustrated together with the inflection point.

[0143] The coefficient of linear expansion α1 of the cured film adhesive of the present invention is preferably 10 to 50 ppm / ℃, more preferably 10 to 40 ppm / ℃, even more preferably 20 to 30 ppm / ℃, and even more preferably 30 to 40 ppm / ℃.

[0144] The coefficient of linear expansion α2 of the cured film adhesive of the present invention is preferably 80 to 200 ppm / ℃, more preferably 100 to 140 ppm / ℃, and even more preferably 100 to 110 ppm / ℃.

[0145] The cured film adhesive of the present invention preferably has a linear expansion coefficient α1 of 10 to 50 ppm / ℃ and a linear expansion coefficient α2 of 80 to 200 ppm / ℃.

[0146] The coefficients of linear expansion α1 and α2 of the film adhesive can be determined by the methods described in the examples.

[0147] The film-like adhesive of the present invention can be formed using the adhesive composition described later. For example, the film-like adhesive of the present invention can be formed as follows: prepare the adhesive composition (varnish) of the present invention, apply the composition to a substrate film that has undergone a demolding treatment, and dry it as needed to form a film-like adhesive.

[0148] When forming the film-like adhesive of the present invention using an adhesive composition containing an organic solvent, the solvent is typically removed from the adhesive composition by drying. Therefore, the solvent content in the film-like adhesive of the present invention is 1000 ppm or less (ppm is a mass basis), typically 0.1 to 1000 ppm.

[0149] As for the substrate film after demolding treatment, it is sufficient for it to function as a cover film for the resulting film-like adhesive; any known substrate film may be used. Examples include demolded polypropylene (PP), demolded polyethylene (PE), and demolded polyethylene terephthalate (PET).

[0150] As a coating method, well-known methods can be appropriately adopted, such as using a roller coater, gravure coater, die coater, reverse coater, etc.

[0151] Regarding drying, as long as the organic solvent can be removed from the adhesive composition without curing the epoxy resin (A) to form a film-like adhesive, it can be done, for example, by maintaining a temperature of 80°C to 150°C for 1 to 20 minutes.

[0152] The film-like adhesive of the present invention can be composed solely of the film-like adhesive of the present invention, or it can be formed by laminating the above-mentioned demolded substrate film to at least one side of the film-like adhesive. Furthermore, it can also be formed by laminating the film-like adhesive with a cutting film to produce a diced chip mounting film. In addition, the film-like adhesive of the present invention can be formed by cutting the film to an appropriate size or by rolling the film into a roll.

[0153] From the perspective of inhibiting the curing of epoxy resin (A), the film adhesive of the present invention is preferably stored at a temperature below 10°C before use (before curing).

[0154] [Composition for Adhesives]

[0155] The adhesive composition of the present invention is an adhesive composition suitable for obtaining the film-like adhesive of the present invention described above. Therefore, the adhesive composition of the present invention contains the epoxy resin (A), epoxy resin curing agent (B), and polymer component (C) described above. The adhesive composition of the present invention may further contain inorganic filler (D), and may also contain additives described as other additives in the film-like adhesive of the present invention.

[0156] The adhesive composition of the present invention is specifically described below.

[0157] An adhesive composition comprising an epoxy resin (A), an epoxy resin curing agent (B), and a polymer component (C), wherein, The polymeric component (C) is an addition polymer or ring-opening polymer obtained through a chain reaction, and has a cyclodextrin structure and adamantyl group in its side chain.

[0158] The adhesive compositions of the present invention typically contain an organic solvent. For example, ethyl methyl ketone is preferred as an organic solvent.

[0159] The total percentage of epoxy resin (A), epoxy resin curing agent (B), and polymer component (C) in the adhesive composition of the present invention can be, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, or 90% by mass or more. Alternatively, this percentage can be 100% by mass or 95% by mass or less.

[0160] The adhesive compositions of the present invention are suitable for use in obtaining the film-like adhesives of the present invention. However, they are not limited to the film-like adhesives of the present invention; for example, they can also be suitably used to obtain liquid or paste-like adhesives.

[0161] The adhesive composition of the present invention can be obtained by mixing the above-mentioned components at a temperature at which the epoxy resin (A) is practically non-curing. The order of mixing is not particularly limited. The resin components, such as epoxy resin (A) and polymer component (C), can be mixed with a solvent as needed, and then the epoxy resin curing agent (B) can be mixed. Here, the polymer component (C) can be mixed separately from the epoxy resin (A), for example, the epoxy resin (A) can be mixed with a solvent as needed, and then the polymer component (C) can be mixed. In any case, mixing in the presence of the epoxy resin curing agent (B) is sufficient as long as it is carried out at a temperature at which the epoxy resin (A) is practically non-curing; mixing of the resin components in the absence of the epoxy resin curing agent (B) can be carried out at a higher temperature.

[0162] In addition, when using inorganic filler (D), there is no particular limitation on the mixing order of inorganic filler (D), and it can be mixed at the same time as epoxy resin curing agent (B).

[0163] From the viewpoint of inhibiting the curing of epoxy resin (A), the adhesive composition of the present invention is preferably stored at a temperature below 10°C before use (before forming a film adhesive).

[0164] Semiconductor packaging and manufacturing methods

[0165] Next, preferred embodiments of the semiconductor packaging and manufacturing method of the present invention will be described in detail with reference to the accompanying drawings. It should be noted that in the following description and drawings, the same or equivalent elements are labeled with the same symbols to omit repetitive descriptions. Figures 1 to 7 This is a schematic longitudinal cross-sectional view illustrating a preferred embodiment of the semiconductor package manufacturing method of the present invention.

[0166] In the semiconductor package manufacturing method of the present invention, firstly, as a first step, as follows: Figure 1 As shown, an adhesive layer (film adhesive 2) is formed by hot-pressing the film adhesive 2 (chip mounting film 2) of the present invention onto the back side of a semiconductor wafer 1 on which at least one semiconductor circuit is formed (i.e., the side of the semiconductor wafer 1 on which no semiconductor circuit is formed). Then, a dicing film 3 (dicing tape 3) is formed through the adhesive layer (film adhesive 2). Figure 1 In this context, the film adhesive 2 is represented as smaller than the cut film 3, but the size (area) of the two films is appropriately set according to the purpose. Regarding the conditions for hot pressing, it is carried out at a temperature where the epoxy resin (A) does not actually undergo heat curing. For example, conditions of approximately 70°C and a pressure of approximately 0.3 MPa can be cited.

[0167] As the semiconductor wafer 1, a semiconductor wafer having at least one semiconductor circuit formed on its surface can be used, such as a silicon wafer, SiC wafer, GaAs wafer, or GaN wafer. In order to apply the film adhesive (chip mounting film) of the present invention to the back side of the semiconductor wafer 1, a known device such as a roller laminator or a manual laminator can be used, for example.

[0168] In the above text, chip mounting film and cutting film were respectively attached. However, when the film adhesive of the present invention is a chip mounting film cutting method, the film adhesive and cutting film can be attached integrally.

[0169] Next, as the second process, such as Figure 2 As shown, by integrally dicing the semiconductor wafer 1 and the adhesive layer (chip mounting film 2), a semiconductor chip 5 with an adhesive layer is obtained on the dicing film 3, comprising a semiconductor chip 4 monolithically formed from the semiconductor wafer and a film-like adhesive sheet 2 monolithically formed from the film-like adhesive 2. There are no particular limitations on the dicing apparatus; any conventional dicing apparatus can be used appropriately.

[0170] Next, as the third step, the semiconductor chip 5 with the adhesive layer is peeled off from the dicing film 3. At this time, the dicing film can be cured using energy rays as needed to reduce adhesive strength. Peeling can be performed by picking up the semiconductor chip 5 with the adhesive layer. Then, as... Figure 3 As shown, a semiconductor chip 5 with an adhesive layer is thermally bonded to a wiring substrate 6 through a film-like adhesive sheet 2, and the semiconductor chip 5 with an adhesive layer is mounted on the wiring substrate 6. As the wiring substrate 6, a substrate with semiconductor circuits formed on its surface can be appropriately used, such as a printed circuit board (PCB), various lead frames, and a substrate with electronic components such as resistors or capacitors mounted on its surface.

[0171] There are no particular limitations on the method of mounting the semiconductor chip 5 with the adhesive layer to the wiring substrate 6, and conventional mounting methods using heat pressing can be appropriately adopted.

[0172] Next, as the fourth step, the adhesive layer (film adhesive sheet 2) is heat-cured. The heat-curing temperature is not particularly limited as long as it is above the initial heat-curing temperature of the film adhesive sheet 2, and is appropriately adjusted according to the type of epoxy resin (A) and epoxy resin curing agent (B) used. For example, 100°C to 180°C is preferred, and 140°C to 180°C is more preferred for curing in a shorter time. If the temperature is too high, the components in the film adhesive sheet 2 tend to easily volatilize and foam during the curing process. The heat-curing time can be appropriately set according to the heating temperature, for example, it can be set to 10 minutes to 120 minutes.

[0173] In the semiconductor package manufacturing method of the present invention, such as Figure 4 As shown, the wiring substrate 6 and the semiconductor chip 5 with adhesive layer are preferably connected via bonding leads 7. There are no particular limitations on such a connection method, and existing known methods can be appropriately used, such as wire bonding methods, TAB (Tape Automated Bonding) methods, etc.

[0174] Alternatively, two or more semiconductor chips can be stacked by thermally bonding and curing another semiconductor chip 4 onto the surface of the mounted semiconductor chip 4, and then connecting it again to the wiring substrate 6 using wire bonding. For example, as shown in... Figure 5 The method shown involves stacking semiconductor chips in a staggered manner; or as... Figure 6 As shown, the bonding wires 7 are embedded while the film-like adhesive sheet 2 after the second layer is thickened and then stacked; etc.

[0175] In the semiconductor package manufacturing method of the present invention, preferably as follows: Figure 7 As shown, a semiconductor package 9 is obtained by encapsulating a wiring substrate 6 and a semiconductor chip 5 with an adhesive layer using a sealing resin 8. There are no particular limitations on the sealing resin 8; any known sealing resin suitable for manufacturing semiconductor packages can be used. Furthermore, there are no particular limitations on the encapsulation method using the sealing resin 8; conventional methods can be employed.

[0176] The semiconductor package of the present invention is manufactured by the semiconductor package manufacturing method described above, wherein at least one part of the semiconductor chip and the wiring substrate, or between the semiconductor chip and the substrate, is bonded by a thermosetting form of the film adhesive of the present invention. Preferably, the semiconductor package of the present invention is a wire-bonded semiconductor package comprising a thermosetting form of the film adhesive of the present invention.

[0177] Example

[0178] The present invention will now be described in more detail based on embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0179] In the examples and comparative examples, room temperature refers to 25°C, MEK is methyl ethyl ketone, and PET is polyethylene terephthalate. Unless otherwise stated, "%" and "parts" are based on mass.

[0180] [Example 1]

[0181] In a 1000 mL detachable flask, 50 parts by weight of HP-7200 (trade name, dicyclopentadiene type epoxy resin, manufactured by DIC) as epoxy resin, 50 parts by weight of YNB-W68 (trade name, addition polymer formed by acryloyl chain polymerization, 50 mol% cyclodextrin modification, 50 mol% adamantane modification, the total percentage of the component with cyclodextrin structure and the percentage of the component with adamantane structure in the total components (mol%): 100 mol%, Tg 45℃, manufactured by YUSHIRO CHEMICAL) as polymer component, and 30 parts by weight of MEK were heated and stirred at 110℃ for 2 hours to obtain a resin varnish.

[0182] The resin varnish was transferred to an 800mL planetary mixer, and 68 parts by weight of silica SO-C2 (trade name, manufactured by Admatechs) and 2 parts by weight of 2PHZ-PW (trade name, imidazole, manufactured by Shikoku Kasei Co., Ltd.) as epoxy resin curing agent were added. After stirring and mixing at room temperature for 1 hour, vacuum degassing was performed to obtain the mixed varnish.

[0183] Next, the obtained mixed varnish was coated onto a 20 μm thick release film (PET film) and dried at 130°C for 10 minutes to obtain a 300 mm long, 200 mm wide film adhesive with a 5 μm thick release film.

[0184] [Example 2]

[0185] In Example 1, the amount of YNB-W68 used was set to 30 parts by mass when preparing the resin varnish, and the amount of SO-C2 used was set to 55 parts by mass when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0186] [Example 3]

[0187] In Example 1, the amount of YNB-W68 used was set to 70 parts by mass when preparing the resin varnish, and the amount of SO-C2 used was set to 80 parts by mass when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0188] [Example 4]

[0189] In Example 1, SO-C2 was not used in the preparation of the mixed varnish, but otherwise a film adhesive with a release film was obtained in the same manner as in Example 1.

[0190] [Example 5]

[0191] In Example 1, the amount of YNB-W68 used was set to 20 parts by mass when preparing the resin varnish, and the amount of SO-C2 used was set to 48 parts by mass when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0192] [Example 6]

[0193] In Example 1, the amount of YNB-W68 used was set to 85 parts by mass when preparing the resin varnish, and the amount of SO-C2 used was set to 90 parts by mass when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0194] [Example 7]

[0195] In Example 1, the amount of YNB-W68 used was set to 95 parts by mass when preparing the resin varnish, and the amount of SO-C2 used was set to 96 parts by mass when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0196] [Example 8]

[0197] In Example 1, when preparing the resin varnish, YNB-W116 (trade name, a polymer component of YNB-W68 with cyclodextrin modification rate adjusted to 80 mol% and adamantane modification rate adjusted to 20 mol%, Tg 45℃, manufactured by YUSHIRO CHEMICAL) was used instead of YNB-W68 as the polymer component. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0198] [Example 9]

[0199] In Example 1, when preparing the resin varnish, YNB-W130 (trade name, a polymer component of YNB-W68 with cyclodextrin modification rate adjusted to 20 mol% and adamantane modification rate adjusted to 80 mol%, Tg 48℃, manufactured by YUSHIRO CHEMICAL) was used instead of YNB-W68 as the polymer component. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0200] [Comparative Example 1]

[0201] In Example 1, YNB-W68 was not used in the resin varnish, and the amount of SO-C2 used was set to 35 parts by weight when preparing the mixed varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0202] [Comparative Example 2]

[0203] In Example 1, when preparing the resin varnish, YNB-W120 (trade name, a polymer component of YNB-W68 with cyclodextrin modification rate adjusted to 0 mol% and adamantane modification rate adjusted to 100 mol%, Tg 40℃, manufactured by YUSHIRO CHEMICAL) was used instead of YNB-W68 as the polymer component. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0204] [Comparative Example 3]

[0205] In Example 1, when preparing the resin varnish, YNB-W121 (trade name, a polymer component of YNB-W68 with cyclodextrin modification rate adjusted to 100 mol% and adamantane modification rate adjusted to 0 mol%, Tg 38℃, manufactured by YUSHIRO CHEMICAL) was used instead of YNB-W68 as the polymer component. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0206] [Comparative Example 4]

[0207] In Example 1, phenoxy resin YP-50 (trade name, Tg 84°C, manufactured by Nippon Steel Chemical Materials Co., Ltd.) was used instead of YNB-W68 when preparing the resin varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 1.

[0208] [Comparative Example 5]

[0209] In Example 4, phenoxy resin YP-50 was used instead of YNB-W68 in the preparation of the resin varnish. Otherwise, a film adhesive with a release film was obtained in the same manner as in Example 4.

[0210] The composition of the film adhesives prepared in each embodiment and comparative example is shown in Table 1. Empty columns indicate that the component is not present.

[0211] For the film adhesives of the above-mentioned embodiments and comparative examples, the warpage, adhesive force, storage modulus, tanδ, and coefficient of linear expansion were determined as follows.

[0212] The results are summarized in Table 1.

[0213] [Determination of warpage]

[0214] The obtained adhesive film with release liner was cut into 100mm long and 100mm wide pieces. Using a manual laminator (trade name: FM-114, manufactured by Technovision), at a temperature of 60°C and a pressure of 0.3MPa, the pieces were adhered to a glass plate 100mm long, 100mm wide, and 0.05mm thick. The release liner was then peeled off the adhesive film to obtain the test specimen. The obtained test specimen was kept in a constant temperature bath at 180°C for 1 hour to allow the adhesive film to heat-cur. After heat curing, the test specimen was removed from the constant temperature bath, cooled to room temperature, and the warpage of the test specimen was measured.

[0215] Warpage was measured as follows: The test specimen was placed on a platform with the adhesive-coated side facing upwards, and the height from the platform surface to the warped end of the specimen was measured using a ruler. When the test specimen was set up as described above, with the center of the specimen in contact with the platform, all four sides of the specimen warped above the platform (on the side with the adhesive-coated side). The warpage was measured on the side opposite to the side with the greatest warpage among the four sides of the specimen. The same measurement was performed on three test specimens, and the average value was calculated.

[0216] [Testing of Adhesion Strength]

[0217] To evaluate the adhesive strength of each film adhesive across the entire temperature range typically exposed during use, the adhesive strength of each film adhesive at 25°C and 150°C was measured as follows.

[0218] For the film adhesives with release films obtained in the various embodiments and comparative examples, firstly, the film adhesives were bonded to one side of a dummy silicon wafer (8-inch size, 0.35mm thick) using a manual laminator (trade name: FM-114, manufactured by Technovision) at a temperature of 70°C and a pressure of 0.3MPa. Then, after peeling the release film from the film adhesive, the dicing tape (trade name: K-13, manufactured by Furukawa Electric Industries, Ltd.) and the dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were bonded to the side of the film adhesive opposite to the dummy silicon wafer (the side with the release film) using the same manual laminator at room temperature and a pressure of 0.3MPa. Next, using a dicing apparatus (trade name: DFD-6340, manufactured by DISCO) equipped with dual-axis dicing blades (Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BC), manufactured by DISCO), dicing is performed from the dummy silicon wafer side in a manner that forms a square with a size of 2mm × 2mm, and a monolithic dummy chip (semiconductor chip) with a film-like adhesive (adhesive layer) is obtained on the dicing film.

[0219] Next, using a die bonder (trade name: DB-800, manufactured by Hitachi High Technology Co., Ltd.), the aforementioned dummy die chip with film adhesive is picked up from the cutting tape. Under the conditions of 130°C, pressure of 0.1MPa (load 400gf) and time of 0.5 seconds, thermoforming is performed so that the film adhesive side of the aforementioned dummy die chip with film adhesive is bonded to the mounting surface side of the lead frame substrate (42Alloy series, manufactured by Toppan Printing Co., Ltd.). Then, it is heated in a dryer at a temperature of 180°C for 1 hour, thereby thermosetting the film adhesive.

[0220] For dummy chips with a film-like adhesive bonded to a substrate, the shear peel force (adhesive force) of the bonded chip to the leadframe substrate was measured using a universal bonding tester (trade name: Series 4000PXY, manufactured by Nordson Advanced Technology). The conditions for the "adhesive force at 25°C" test were set as follows: stage temperature 25°C, head height 25 μm, and speed 0.5 mm / sec.

[0221] The conditions for the "150℃ adhesion force" test were set as follows: stage temperature 150℃, head height 25μm, and speed 0.5mm / sec.

[0222] The results are shown in Table 1. The film adhesives of Comparative Examples 1 and 5 peeled off under the above-mentioned "150°C adhesion strength" test conditions, and the shear adhesion strength could not be measured. Therefore, "-" is recorded in the "150°C adhesion strength" column of Comparative Examples 1 and 5 in Table 1.

[0223] [Storage modulus, tanδ]

[0224] The film-like adhesives with release films obtained in each embodiment and comparative example were cured at 180°C for 1 hour, cut into 5mm × 17mm pieces, and the release films were peeled off to obtain test specimens of the cured film-like adhesives. For the obtained test specimens, dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (trade name: Rheogel-E4000F, manufactured by UBM Corporation) under the conditions of a measurement temperature range of 20–300°C, a heating rate of 5°C / min, and a frequency of 1Hz (tensile mode). The storage modulus and loss modulus at each temperature were measured. The storage modulus at 25°C was determined. Furthermore, the loss tangent tanδ at 25°C was calculated from the storage modulus and loss modulus at 25°C. The above measurements were performed according to JIS K7244-4:1999.

[0225] [Determination of the coefficient of linear expansion]

[0226] The film-like adhesives with release films obtained in each embodiment and comparative example were cured at 180°C for 1 hour, cut into 5mm × 17mm (200μm thickness) pieces, and the release film was peeled off to obtain test specimens of the cured film-like adhesive. For the obtained test specimens, thermomechanical analysis was performed using a thermomechanical analysis apparatus (trade name: TMA7000, manufactured by Hitachi High Technology Co., Ltd.) under the conditions of a measurement temperature range of 20–250°C, a heating rate of 5°C / min, and a weight of 9.8g (tensile mode). The point where the slope of the obtained measurement curve changed was taken as the inflection point. The coefficient of linear expansion closer to the inflection point was taken as α1, and the coefficient of linear expansion closer to the inflection point was taken as α2. The coefficients of linear expansion α1 and α2 were calculated by the following formulas. The determination of the coefficient of linear expansion was performed according to JIS K7197:2012.

[0227] α = (1 / L) × (dL / dT)

[0228] α: Coefficient of linear expansion

[0229] L: Length of the test subject

[0230] dL: Change in the length of the test specimen

[0231] dT: The change in temperature of the test specimen

[0232] The results of the above experiments are shown in the table below.

[0233] [Table 1]

[0234] Table 1

[0235]

[0236] In the table above, the values ​​recorded in the columns for "Polymer Components", "Epoxy Resin", "Inorganic Filler" and "Epoxy Resin Curing Agent" are all in parts by mass.

[0237] In the polymer components, "C:50, A:50" means that the cyclodextrin modification rate of the polymer components is 50 mol% and the adamantane modification rate is 50 mol%.

[0238] "C:80, A:20" means that the cyclodextrin modification rate of the polymer component is 80 mol% and the adamantane modification rate is 20 mol%.

[0239] "C:20, A:80" means that the cyclodextrin modification rate of the polymer components is 20 mol% and the adamantane modification rate is 80 mol%.

[0240] "C:0, A:100" means that the cyclodextrin modification rate of the polymer component is 0 mol% and the adamantane modification rate is 100 mol%.

[0241] "C: 100, A: 0" means that the cyclodextrin modification rate of the polymer component is 100 mol% and the adamantane modification rate is 0 mol%.

[0242] The film adhesive of Comparative Example 1 does not contain polymer components. This film adhesive exhibits a poor adhesion strength of 10 MPa at 25°C.

[0243] The polymer components of the film adhesives in Comparative Examples 2-4 were polymers or phenoxy resins that did not possess either a cyclodextrin structure or adamantyl groups. As a result, these film adhesives exhibited warpage of more than 5 mm.

[0244] The film adhesive of Comparative Example 5 exhibited a sufficient adhesive force of 30 MPa at 25°C, but peeled off at 150°C, resulting in poor overall adhesive strength. It is believed that the film adhesive of Comparative Example 5 has relatively large coefficients of linear expansion α1 and α2, and the coefficients of linear expansion change significantly with temperature, thus causing the adhesive strength to decrease at 150°C.

[0245] In contrast, the film adhesives of Examples 1 to 9, which meet the requirements of this invention, exhibit warpage of 0 to 3 mm, an adhesive strength of 15 MPa or more at 25°C, and an adhesive strength of 15 MPa or more at 150°C. It is evident that by using the film adhesive of this invention, a semiconductor package with reduced warpage can be formed without significantly impairing the adhesive strength to the adherend. Furthermore, it is also evident that sufficiently high adhesive strength is achieved regardless of the presence or absence of inorganic fillers (comparison between Examples 1 and 4). Further, it is evident that the adhesive strength of the film adhesive of this invention does not easily decrease even at high temperatures of around 150°C.

[0246] The invention has been described together with its embodiments, but unless otherwise specified, we do not intend to limit our invention to any of the details described, and it should be interpreted broadly without departing from the spirit and scope of the invention as shown in the appended claims.

[0247] This application claims priority based on Japanese Patent Application No. 2024-053902 filed on March 28, 2024, the contents of which are incorporated herein by reference and are incorporated as part of the description herein.

[0248] Explanation of reference numerals in the attached figures

[0249] 1. Semiconductor wafer

[0250] 2. Adhesive layer (film adhesive)

[0251] 3. Cutting membrane (cutting tape)

[0252] 4. Semiconductor chips

[0253] 5 Semiconductor chips with film-like adhesive sheets

[0254] 6 Wiring substrate

[0255] 7 Bonding wires

[0256] 8. Sealing resin

[0257] 9 Semiconductor Packaging

Claims

1. A film-like adhesive comprising epoxy resin (A), epoxy resin curing agent (B), and polymer component (C), wherein, The polymeric component (C) is an addition polymer or ring-opening polymer obtained through a chain reaction, and has a cyclodextrin structure and adamantyl group in its side chain.

2. The film-shaped adhesive agent according to claim 1, wherein In the total solids composition of the film adhesive, the content of the polymer component (C) is 15% to 90% by mass.

3. The film-shaped adhesive agent according to claim 1 or 2, wherein The component having a cyclodextrin structure accounts for 20 mol% to 80 mol% of all components of the polymer (C), and the component having an adamantyl group accounts for 20 mol% to 80 mol% of all components of the polymer (C).

4. The film-shaped adhesive according to any one of claims 1 to 3, wherein The polymer component (C) is an addition polymer formed by chain polymerization of (meth)acryloyl groups or an open-ring polymer formed by chain polymerization of epoxy groups.

5. The film-shaped adhesive agent according to any one of claims 1 to 4, wherein The epoxy resin (A) comprises a dicyclopentadiene type epoxy resin.

6. The film adhesive according to any one of claims 1 to 5, wherein it contains an inorganic filler (D).

7. The film-shaped adhesive according to any one of claims 1 to 6, wherein The storage modulus of the cured product formed by curing the film adhesive is 0.1 GPa to 1.0 GPa.

8. The film adhesive according to any one of claims 1 to 7, wherein, The tanδ of the cured product formed by curing the film adhesive is 0.2 to 1.

2.

9. The film adhesive according to any one of claims 1 to 8, wherein, The coefficient of linear expansion α1 of the cured product formed by curing the film adhesive is 10ppm / ℃~50ppm / ℃.

10. The film adhesive according to any one of claims 1 to 9, wherein, The cured product formed by curing the film adhesive has a linear expansion coefficient α1 of 10ppm / ℃ to 50ppm / ℃ and a linear expansion coefficient α2 of 80ppm / ℃ to 200ppm / ℃.

11. The film adhesive according to any one of claims 1 to 10, wherein, The thickness of the film adhesive is 1 μm to 100 μm.

12. An adhesive composition comprising an epoxy resin (A), an epoxy resin curing agent (B), and a polymeric component (C), wherein, The polymeric component (C) is an addition polymer or ring-opening polymer obtained through a chain reaction, and has a cyclodextrin structure and adamantyl group in its side chain.

13. A chip dicing and mounting film, which is formed by laminating the film-like adhesive according to any one of claims 1 to 11 with a dicing film.

14. A method for manufacturing a semiconductor package, comprising: In the first step, an adhesive layer is formed by hot-pressing the film adhesive according to any one of claims 1 to 11 onto the back side of a semiconductor wafer on which a semiconductor circuit is formed on the surface, and a cutting film is formed through the adhesive layer. In the second step, the semiconductor wafer and the adhesive layer are integrally cut to obtain a semiconductor chip with an adhesive layer having a film-like adhesive sheet and a semiconductor chip on the cut film. In the third step, the semiconductor chip with the adhesive layer is peeled off from the dicing film, and the semiconductor chip with the adhesive layer is thermally bonded to the wiring substrate through the adhesive layer; and The fourth step involves heat curing the adhesive layer.

15. A wire-bonded semiconductor package comprising a thermosetting form of the film adhesive according to any one of claims 1 to 11.

Images