Adhesive composition, thin film adhesive using the same and semiconductor package, and method for manufacturing semiconductor package

Abstract

An adhesive composition containing at least an epoxy resin (A), an epoxy resin curing agent (B), and a high molecular component (C), wherein the storage modulus after curing is 2000 MPa or less, and the loss tangent is 0.03 or more, and the bonding strength when the cured compositions are bonded to each other is 5 MPa or more. [The storage modulus and the loss tangent after curing are measured by preparing a thin film-shaped adhesive sheet of 5 mm x 17 mm x 200 µm by heat-curing the adhesive composition at 180°C for 1 hour, and measuring in a temperature range of 20 to 300°C at a temperature increase rate of 5°C / min and a frequency of 1 Hz. At this time, the measurement values at the following bonding temperatures are sampled.][Bonding temperature: any temperature of 25°C or higher and 300°C or lower]

Description

Technical Field

[0001] This invention relates to adhesive compositions, thin-film adhesives using the same, semiconductor packages, and methods for manufacturing semiconductor packages. Background Technology

[0002] With the development of miniaturization, lightweighting, and high performance in electronic devices, there is a growing demand for high integration of semiconductor chips and other components. However, there are limits to the miniaturization of circuits. In recent years, a method has been proposed to achieve high integration by vertically stacking multiple substrates (wafers), semiconductor chips, and other components to construct a multi-layered three-dimensional structure. A representative example is a semiconductor package that is stacked on a 2.XD package formed by housing and mounting individual semiconductor chips on a Si interposer or an RDL interposer.

[0003] Traditionally, substrates and semiconductor chips within semiconductor packages have been highly integrated using bump bonding. However, to further shorten the interconnect wiring distance, a direct bonding method for directly bonding Cu interconnects is needed. Direct bonding methods based on resin mixing or inorganic material mixing are being researched, but due to concerns about foreign matter control and cost associated with inorganic mixing, the focus is now on resin mixing.

[0004] There are known methods of bonding, for example, using a composition as a so-called resin mixing method for direct bonding materials, where the composition is obtained by spin-coating a composition containing an amic acid crosslinked silane compound onto a wafer, drying and curing it to become an imide crosslinked siloxane (e.g., Patent Documents 1 and 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-182621

[0008] Patent Document 2: International Publication No. 2020 / 085183 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] In direct bonding methods, insufficient adhesive strength after bonding is a problem. This is believed to be due to uneven bonding layer thickness or voids present during bonding. It is speculated that spin coating methods described in existing technical literature suffer from difficulties in controlling thickness accuracy due to variations in rotation speed, material viscosity, and drying speed, leading to uneven adhesive strength. Therefore, the present invention aims to provide a thin-film adhesive and its composition, which enables void-free bonding during semiconductor wafer bonding, controls thickness unevenness, and achieves sufficient adhesive strength and bonding reliability. Furthermore, the present invention aims to provide a semiconductor package using the aforementioned thin-film adhesive, and a method for manufacturing the semiconductor package.

[0011] Solution for solving the problem

[0012] The inventors have conducted various tests and verifications on this adhesive and adhesive composition. Tests included parameters such as physical properties, chemical properties, and physicochemical properties, and a large amount of data was collected and analyzed. The results were carefully compiled and verified, revealing that when preparing a film-like adhesive, the aforementioned objectives can be achieved by maintaining a storage modulus of 2000 MPa or less at the bonding temperature and a loss tangent of 0.03 or more. Furthermore, achieving good adhesion and a bond strength of 5 MPa or more is a necessary condition when preparing a film-like adhesive. Moreover, it has been found that the aforementioned objectives can be achieved more accurately by setting the epoxy equivalent of the epoxy resin to a suitable range, or by setting the mixing ratio of liquid epoxy resin to solid epoxy resin to a suitable range. This invention is derived from these insights and has the following structure.

[0013] (1) An adhesive composition comprising at least an epoxy resin (A), an epoxy resin curing agent (B), and a polymeric component (C), characterized in that,

[0014] The storage modulus after curing is 2000 MPa or less, and the loss tangent is 0.03 or more under the following conditions. The bond strength of the cured compositions when bonded together under the following conditions is 5 MPa or more.

[0015] [The storage modulus and loss tangent after curing were measured by heat curing the adhesive composition at 180°C for 1 hour to form a 5mm×17mm×200μm film-like adhesive sheet. The measurement was performed at a temperature range of 20–300°C, a heating rate of 5°C / min, and a frequency of 1Hz. The measured values ​​at the following bonding temperatures were sampled.]

[0016] [Joint temperature: any temperature above 25°C and below 300°C],

[0017] [The bonding strength is the strength of two chips with a 1.0 μm thick thin film adhesive bonded together at a bonding temperature and then peeled off at room temperature. The thin film adhesive is made by heating the adhesive composition at 180°C for 1 hour to thermally cure it.]

[0018] (2) The adhesive composition according to (1), characterized in that,

[0019] The epoxy resin (A) used in the adhesive composition has an epoxy equivalent of 300 g / eq or more, and the content of the epoxy resin (A) is 20% by mass or more of the total amount of epoxy resin (A), epoxy resin curing agent (B), and polymer component (C).

[0020] (3) The adhesive composition according to (1), characterized in that,

[0021] The epoxy resin (A) is formed by mixing liquid epoxy resin and solid epoxy resin at room temperature. When the polymer component (C) is set to 100 parts by mass, the content of the liquid epoxy resin is 100 to 250 parts by mass, the content of the solid epoxy resin is 15 to 90 parts by mass, and the mass ratio of the solid epoxy resin to the liquid epoxy resin is in the range of 1:10 to 6:10.

[0022] (4) The adhesive composition according to (1), characterized in that,

[0023] The epoxy resin curing agent (B) is an imidazole curing agent.

[0024] (5) The adhesive composition according to claim 1, characterized in that,

[0025] The bonding temperature is above 25°C and below 200°C.

[0026] (6) A film-like adhesive, characterized in that it is formed by heat treatment of the adhesive composition of any one of (1) to (5).

[0027] (7) The film adhesive according to (6), characterized in that,

[0028] The thickness is 0.1–50 μm.

[0029] (8) A method for manufacturing a semiconductor package, characterized in that an adhesive layer is formed by bonding and thermally curing the thin film adhesive (6) on a semiconductor wafer having at least one semiconductor circuit formed on its surface, and the semiconductor wafer is bonded and stacked by the adhesive layer, and the semiconductor wafer is multilayered by using a resin cured body formed by directly pressing the adhesive layer at room temperature or by further thermal curing and pressing.

[0030] (9) The method for manufacturing a semiconductor package according to (8) is characterized by comprising the following steps:

[0031] The terminals are exposed from the adhesive layer, and the adhesive layer is planarized so that the surface of the adhesive layer is coplanar with the surface of the terminals.

[0032] (10) A semiconductor package, characterized in that it is composed of a semiconductor wafer formed by bonding a resin cured body using the thin-film adhesive described in (6).

[0033] (11) A film-like adhesive, formed by heat-treating an adhesive composition containing at least epoxy resin (A), epoxy resin curing agent (B), and polymeric component (C), characterized in that,

[0034] The energy storage modulus is below 2000 MPa and the loss tangent is above 0.03 under the following conditions, and the bonding strength is above 5 MPa under the following conditions during bonding.

[0035] [Storage modulus and loss tangent were measured by thermosetting the adhesive composition at 180°C for 1 hour to form a 5mm × 17mm × 200μm thin film adhesive sheet, under the conditions of a measurement temperature range of 20–300°C, a heating rate of 5°C / min, and a frequency of 1Hz. The measured values ​​at the following bonding temperatures were sampled.]

[0036] [Joint temperature: any temperature above 25°C and below 300°C],

[0037] [The bonding strength is the strength of two chips coated with a 1.0 μm thick thin film adhesive, bonded together at the bonding temperature, when peeled off at room temperature.]

[0038] Invention Effects

[0039] The adhesive composition or film-like adhesive of the present invention enables gapless bonding when bonding semiconductor wafers, and allows for control of thickness unevenness, resulting in sufficient adhesive force and bonding reliability. Furthermore, semiconductor packages using the film-like adhesive of the present invention exhibit high quality and good performance reliability. Moreover, the manufacturing method of the present invention allows for the suitable manufacture of semiconductor packages incorporating the aforementioned film-like adhesive. Attached Figure Description

[0040] Figure 1 This is a flowchart illustrating the manufacturing process and application process of film-like adhesives.

[0041] Figure 2This is a cross-sectional view schematically illustrating the manufacturing process of a semiconductor wafer according to one embodiment of the present invention.

[0042] Figure 3 It is shown schematically. Figure 1 (d) A cross-sectional view of the grinding-based planarization process used in the planarization process.

[0043] Figure 4 This is a schematic side view showing two substrates with a thin film adhesive attached joined together by abutting the adhesive film.

[0044] Figure 5 It is a photograph obtained by taking a microscopic image of the state in which the thin film adhesive is bonded together, viewed from the side.

[0045] Figure 6 This is a side view schematically illustrating the apparatus and measurement configuration for measuring chip shear strength. Detailed Implementation

[0046] The adhesive composition of the present invention is characterized in that it contains at least epoxy resin (A), epoxy resin curing agent (B), and polymer component (C), and the cured composition has a storage modulus of 2000 MPa or less and a loss tangent of 0.03 or more, and the bond strength of the cured composition when bonded together is 5 MPa or more. The present invention will now be described in detail with a focus on preferred embodiments and examples, and with reference to the accompanying drawings as needed.

[0047] Regarding the adhesive composition of the present invention, the storage modulus and loss tangent after curing are values ​​measured by forming a thin film adhesive sheet of 5 mm × 17 mm × 200 μm. The measurement temperature (sampling temperature) is the bonding temperature. The bonding temperature refers to the temperature at which a substrate, etc., is bonded by the thin film adhesive, preferably 25°C or higher and 300°C or lower, typically in the range of room temperature (25°C) to 200°C. Under the condition that the storage modulus (E') is 2000 MPa or lower and the bonding temperature is 25°C (except in the case of no filler), it is preferably 1800 MPa or lower, more preferably 1600 MPa or lower. As a lower limit value, there is no particular limitation, but it is practical to be 1000 MPa or higher. Under the condition of bonding temperature of 200°C or without filler, the storage modulus is preferably 200 MPa or lower, more preferably 150 MPa or lower, and particularly preferably 100 MPa or lower. The lower limit value is not particularly limited, but it is preferably 1 MPa or higher, more preferably 2 MPa or higher, and even more preferably 5 MPa or higher.

[0048] The adhesive composition of the present invention has a loss tangent of 0.03 or more in the cured film adhesive, preferably 0.04 or more, and more preferably 0.05 or more. No particular upper limit is imposed, but values ​​of 1.0 or less are practical. Furthermore, the cured film adhesive refers to a film adhesive obtained by treating the film adhesive under the conditions of heat treatment 2 or heat treatment 3 described later.

[0049] When the adhesive composition of the present invention is formed into a cured film adhesive, it possesses the aforementioned storage modulus and loss tangent, thereby exhibiting good adhesion and minimizing the formation of voids or other irregularities at the bonding interface. Furthermore, the substrate surface can have unevenness such as terminals. While film adhesives may not conform to their shape, by setting the storage modulus E' and loss tangent tanδ within the aforementioned suitable range when forming the film, appropriate conformability and adhesion to the substrate are achieved, suppressing void formation even at protruding terminal portions. The storage modulus primarily aims at morphological stability and flexibility, defining a range within which these characteristics are not lost. The loss tangent primarily indicates the relationship with adhesion; if it exceeds a certain value, it exhibits characteristics of delayed deformation and conforming to the unevenness of the substrate.

[0050] The adhesive composition of the present invention has a cured bond strength of 5 MPa or more, preferably 10 MPa or more, more preferably 15 MPa or more, even more preferably 20 MPa or more, even more preferably 25 MPa or more, even more preferably 30 MPa or more, and even more preferably 35 MPa or more. A higher bond strength results in stronger bonding with the semiconductor chip. Bond strength refers to the strength required when a dummy chip coated with a cured film-like adhesive is brought into contact with another dummy chip coated with a cured film-like adhesive at a bonding temperature using the adhesive surfaces, and then peeled off at room temperature (25°C). No specific upper limit is imposed on the bond strength, but 100 MPa or less is practically acceptable.

[0051] For example, the bonding temperature can be defined as the temperature at which an adhesive composition is cured at 180°C for 1 hour to form a thin-film adhesive, and the substrate is bonded using this thin-film adhesive. The specific temperature is not limited, but is preferably 25°C to 300°C, more preferably 25°C to 200°C. In a preferred embodiment of the invention, it is sufficient to satisfy predetermined conditions (E', tanδ, bonding strength) at any of the above bonding temperatures. Preferably, the predetermined conditions are satisfied at at least one of 300°C (preferably 200°C) and 25°C, more preferably at 300°C (preferably 200°C), and even more preferably at 25°C. Particularly, this is preferred because it reduces the likelihood of positional shift during bonding at room temperature.

[0052] The samples for measuring various parameters can be properly prepared, but in this invention, it is preferred to use samples that have been heat-treated under the following conditions.

[0053] • When bonding at room temperature (25°C) and measuring viscoelastic properties: Heat treatment 1 [130°C for 1.5 minutes] *1 Heat treatment 2 [70℃, 0.3MPa pressure] *1 180℃ for 1 hour

[0054] • At a bonding temperature of 200°C: Heat treatment 1 [130°C for 1.5 minutes] *1 Heat treatment 2 [70℃, 0.3MPa pressure] *1 180℃ for 1 hour, heat treatment 3 at 200℃, 10N / 40N *2 10 seconds

[0055] *1 [ ] can be omitted

[0056] *2 Chip shear strength measurement: 10N; Bondability evaluation: 40N

[0057] (Epoxy Resin (A))

[0058] The adhesive composition of the present invention contains epoxy resin (A), epoxy resin curing agent (B), and polymer component (C). Epoxy resin (A) is classified as solid epoxy resin and liquid epoxy resin at room temperature (25°C). In the adhesive composition of the present invention, a mixture of solid epoxy resin and liquid epoxy resin or containing only liquid epoxy resin is preferred, and a mixture of solid epoxy resin and liquid epoxy resin is more preferred. If only liquid epoxy resin is contained, the viscosity may be too strong, making it difficult to handle. Furthermore, a mixture of both makes it easier to balance appropriate conformability and morphological stability. Specific examples of epoxy resin include solid BisA type epoxy resin, liquid flexible epoxy resin, and liquid BisA type epoxy resin, among which a combination of solid BisA type epoxy resin and liquid flexible epoxy resin is preferred.

[0059] The viscosity of epoxy resin at room temperature (25°C) can be used to define whether the epoxy resin is liquid or solid. Liquid epoxy resin is preferably 50 Pa·s or less, more preferably 40 Pa·s or less, and even more preferably 30 Pa·s or less. The lower limit is not particularly limited, but is preferably 0.5 Pa·s or more, more preferably 0.8 Pa·s or more, and even more preferably 1.0 Pa·s or more. As an upper limit, if the viscosity of the liquid epoxy resin is within this range, it has moderate fluidity, making it easy to process. Furthermore, when forming a thin-film adhesive, it follows the contours of the substrate, which is preferred. On the other hand, the viscosity of solid epoxy resin exceeds 50 Pa·s. Furthermore, the viscosity measurement method is based on section 8 of JIS Z 8803:2011, "Viscosity Measurement Method Using a Coaxial Duplex Rotational Viscometer." As the measuring device, a precision rotational viscometer RSX-CC (manufactured by Eiko Seiki Co., Ltd.) was used.

[0060] The epoxy equivalent of epoxy resin (A) is preferably 200 g / eq or more, more preferably 300 g / eq or more, and even more preferably 350 g / eq or more. No particular upper limit is set, but 1000 g / eq or less is practical. By ensuring the epoxy equivalent of epoxy resin (A) is within the above range, moderate flexibility and preferred adhesion of the film adhesive can be obtained, and excellent performance can be achieved in terms of bonding and chip shear strength.

[0061] The molecular weight of the solid epoxy resin is not particularly limited, but is preferably 700 or more, more preferably 800 or more, and even more preferably 900 or more. As an upper limit, it is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less. If the molecular weight of the solid epoxy resin is within this range, it is easy to maintain its shape, and a film-like adhesive that is not too hard and has moderate elasticity can be produced. The molecular weight of the liquid epoxy resin is not particularly limited, but is preferably more than 400, more preferably 450 or more, and even more preferably 470 or more. The upper limit is not particularly limited, but is preferably 800 or less, more preferably 700 or less, and even more preferably 650 or less. It is preferred that the molecular weight of the liquid epoxy resin is within the above range, especially in combination with the solid epoxy resin, to achieve moderate flexibility in the film-like adhesive. The specifications of the epoxy resins used in the examples are listed in Table 1 below.

[0062] Furthermore, unless otherwise specified in this specification, the molecular weight is a value (weight average molecular weight) obtained by conversion of polystyrene based on GPC (Gel Permeation Chromatography). No special limitations are imposed on the conditions; for example, tetrahydrofuran is used as the carrier, and two TSKgel GMHXL columns and one G2500HXL column (φ7.8mm × 30cm, Tosoh manufacture) are used, with a flow rate of 1 mL / min, a column temperature of 40°C, and an injection volume of 0.2 mL. For cases where the molecular weight is too low to be measured by GPC, mass spectrometry (MS) can be used for identification.

[0063] Table 1

[0064]

[0065] The softening point of the solid epoxy resin is not particularly limited, but is preferably 60°C or higher, more preferably 70°C or higher, and even more preferably 75°C or higher. As an upper limit, it is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower. With the softening point of the solid epoxy resin within the above range, the film-like adhesive will not flow out or deform when mixed with the liquid epoxy resin, which is preferred. The softening point of the liquid epoxy resin is preferably 40°C or lower, more preferably 35°C or lower, and even more preferably 30°C or lower. With the softening point of the liquid epoxy resin within the above range, the stability of the film-like adhesive's morphology and its conformability to the substrate can be obtained when mixed with the solid epoxy resin, which is preferred.

[0066] In this specification, the softening point refers to the value measured based on the softening point test (ring and ball method) (according to measurement conditions: JIS-K7234-1986).

[0067] An example of an epoxy resin that can be used in this invention is shown below. However, this invention is not to be limited thereto. n represents an integer, preferably 0 to 2. R is a hydrogen atom or a methyl group.

[0068] [Chemical Formula 1]

[0069]

[0070] In the adhesive composition of the present invention, when the polymer component (C) is set to 100 parts by weight, the amount of epoxy resin (solid and liquid components combined) is preferably 150 parts by weight or more, more preferably 175 parts by weight or more, and even more preferably 190 parts by weight or more. As an upper limit, it is preferably 250 parts by weight or less, more preferably 230 parts by weight or less, and even more preferably 210 parts by weight or less. By formulating the epoxy resin within this range, both sufficient adhesive strength and morphological stability can be maintained, which is preferred.

[0071] The amount of epoxy resin (A) in the formulation relative to the total amount of epoxy resin (A), epoxy resin curing agent (B), and polymer component (C) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. As an upper limit, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0072] The amount of epoxy resin (A) in the formulation, when containing fillers, is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, relative to the total amount of the adhesive composition. As an upper limit, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. When not containing fillers, it is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to the total amount of the adhesive composition. As an upper limit, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0073] In the adhesive composition of the present invention, a mixture of liquid epoxy resin (particularly sometimes also called liquid flexible epoxy resin or stress-relaxation epoxy resin) and solid epoxy resin is preferred. When the epoxy resin (A) is a mixture of liquid epoxy resin and solid epoxy resin at room temperature, and the polymer component (C) is set to 100 parts by weight, the amount of liquid epoxy resin is preferably 100 to 250 parts by weight, more preferably 115 to 200 parts by weight, and even more preferably 120 to 180 parts by weight. When the polymer component (C) is set to 100 parts by weight, the content of solid epoxy resin is preferably 15 to 90 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 25 to 70 parts by weight. The mass ratio of solid epoxy resin to liquid epoxy resin is preferably in the range of 0.5:10 to 9:10, more preferably in the range of 0.75:10 to 8:10, even more preferably in the range of 1:10 to 6:10, and even more preferably in the range of 1.5:10 to 4.5:10.

[0074] The content of stress-relaxation epoxy resin (liquid flexible epoxy resin) relative to the total resin of epoxy resin (A) and polymer component (C) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. As an upper limit, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. Typically, the liquid-resistant epoxy resin is an epoxy resin that maintains a flexible skeleton in the dotted-line portion as described below. Therefore, it imparts stress-relaxation capability. Indirectly, in this invention, it has the effect of reducing the storage modulus, an important parameter, or increasing the loss tangent. Through this effect, thickness unevenness can be controlled when forming a thin-film adhesive, and sufficient adhesion and bonding reliability can be obtained.

[0075]

Chemical Formula 2

[0076]

[0077] If the mixing ratio of solid epoxy resin and liquid epoxy resin is within the above-mentioned range, morphological stability can be ensured when forming a film-like adhesive. Furthermore, flexibility is preferred, allowing it to conform to the unevenness of the substrate for bonding. Additionally, the above-mentioned range is also preferred in achieving excellent adhesion when forming a film-like adhesive. Moreover, with moderate adhesion, the manufacturing process is smooth.

[0078] The adhesive composition of this embodiment is intended to be thin-filmed and applied to a substrate. The conditions for forming the adhesive composition into a thin-film adhesive are not particularly limited; for example, the necessary components can be dissolved in a solvent to form a softened varnish or even a mixed varnish, and then heated at a predetermined temperature for a predetermined time to evaporate the solvent, thereby obtaining a thin-film adhesive (see reference). Figure 1 (1) Heat treatment. In this embodiment, by employing this film-forming process and the subsequent thermosetting process (heat treatment 2), an adhesive layer with a less uneven and more uniform surface, which is impossible to achieve with liquid adhesives, can be obtained. Conversely, in the above-mentioned film-forming process, the composition of the adhesive composition selected to form a suitable film is crucial. Furthermore, the above-mentioned heat treatment process will be described in detail in the following description of the manufacturing method.

[0079] Epoxy resin (A) may be used in one or more forms. When using two or more forms, the total amount shall be within the range described above.

[0080] (Epoxy resin curing agent (B))

[0081] As curing agents for epoxy resins, conventionally used curing agents can be used. Examples include amines (aliphatic amines, aromatic amines, modified amines), polyamide resins, tertiary and secondary amines, imidazoles, polythiol curing agents, liquid polythiols, polysulfide resins, and acid anhydrides. In this invention, imidazoles are particularly preferred. As imidazole curing agents, the following compounds can be listed. Among them, compound (e) is preferred. Furthermore, R in the formula is a hydrogen atom or an organic group.

[0082]

Chemical Formula 3

[0083]

[0084] The amount of epoxy resin curing agent (B) can be appropriately determined according to the amount of epoxy resin. For example, it is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of polymer component (C), more preferably 1 to 6 parts by mass, and particularly preferably 2 to 4 parts by mass. It is preferable that the epoxy resin curing agent (B) is formulated within the above range so that the epoxy resin reacts appropriately and undergoes crosslinking.

[0085] Epoxy resin curing agent (B) may be used in one or more forms. When using two or more forms, the total amount shall be within the range described above.

[0086] (Polymer component (C))

[0087] The polymeric component (C) is the component that forms the basic framework when the adhesive composition of the present invention is made into a film-like adhesive. When the total mass percentage of the epoxy resin (A), epoxy resin curing agent (B), and polymeric component (C) is 100%, the content of polymeric component (C) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass. The polymer constituting the polymeric component can be used without limitation, for example, BisA type phenoxy resins, polyurethane resins, acrylic resins, etc. The molecular weight of the polymeric component is not particularly limited; compounds with a molecular weight of 20,000 to 1,000,000, preferably 35,000 to 800,000, more preferably 50,000 to 600,000, are listed. By setting the molecular weight of the polymeric component (C) to the lower limit value or above, a stable form can be obtained when making a film-like adhesive. By setting the molecular weight below the aforementioned upper limit, it is possible to obtain a flexible structure that follows the contours (terminals) of the substrate surface and exhibits good adhesion. Furthermore, the method for measuring the molecular weight is as described above.

[0088] The polymer component (C) may be one type or two or more types. If two or more types are used, the total amount shall be within the range described above.

[0089] (filler)

[0090] In the adhesive composition of the present invention, silica, talc, calcium carbonate, etc., can be introduced as fillers as needed, with silica being preferred. This, in particular, improves the storage modulus and enables good morphological stability when the adhesive is made into a film. The amount of filler is not particularly limited; when the total adhesive composition is set to 100% by mass, it is preferably 15% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and even more preferably 25% by mass or more and 65% by mass or less.

[0091] One type of packing material may be used, or two or more types may be used. When two or more types are used, the total amount shall be within the range described above.

[0092] (Silane coupling agent)

[0093] Silane coupling agents are compounds used to combine with fillers (e.g., silica) to obtain stability within the system; therefore, they can be selected based on the amount and type of filler used. Furthermore, the adhesive composition of the present invention uses epoxy resin, therefore, affinity in this respect is preferred. Depending on the relevant circumstances, the silane coupling agent used in the adhesive composition of the present invention is preferably an epoxysilane-type silane coupling agent. Specifically, it is preferred to be a compound with an epoxy group (epoxyethylene alkyl) introduced at one or both ends of the polysiloxane. The amount of silane coupling agent prepared relative to 100 parts by weight of the polymeric component (C) is preferably 0.5 to 6 parts by weight, more preferably 0.8 to 4 parts by weight, and particularly preferably 1 to 3 parts by weight. This range of silane coupling agent ensures that other properties are not affected, and that the silica particles used as fillers remain within the system without causing uneven distribution or shedding of silica, which is therefore preferred.

[0094] One or more silane coupling agents may be used. When using more than two, the total amount shall be within the range described above.

[0095] (solvent)

[0096] The solvent used in the adhesive composition of the present invention is not particularly limited, as long as it can dissolve or even disperse the epoxy resin (A), epoxy resin curing agent (B), and polymer component (C) as the above-mentioned components. Preferably, it is an organic solvent, including alcohols, ketones (such as methyl ethyl ketone (MEK), acetone, etc.), cyclic or chain hydrocarbons (such as cyclohexane, etc.), aldehydes, and carbonates (such as dimethyl carbonate, etc.). The boiling point of the organic solvent is not particularly limited, but from the perspective of not evaporating at room temperature and appropriately evaporating in the above-mentioned heat treatment 1, the boiling point is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. As an upper limit, it is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower. One solvent or two or more solvents may be used.

[0097] (Thin film adhesives, semiconductor packaging manufacturing methods)

[0098] The film-like adhesive of the present invention is obtained using an adhesive composition having the above-described components. Figure 1 An example of the manufacturing process of the film-like adhesive and the process of forming the adhesive layer for bonding the film-like adhesive is shown. The method of forming the adhesive composition into a film-like adhesive is not particularly limited; for example, the following methods can be listed: preparing a varnish having the necessary components or a mixed varnish with added fillers, and heating it on a release film or the like for a certain time. The heating temperature used for this heat treatment 1 is preferably 80°C to 150°C, more preferably 90°C to 140°C, and even more preferably 100°C to 135°C. The heating time (dwell time) is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 20 minutes, and even more preferably 30 seconds to 15 minutes. If the adhesive composition is overheated when forming the film-like adhesive, the adhesiveness of the film-like adhesive may continue to deteriorate. On the other hand, if the heating is insufficient, the surface morphology may be unstable, and the adhesion and bonding strength may be abnormal. The thickness of the film-like adhesive is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 0.75 μm or more. As an upper limit, it is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0099] A method for manufacturing a package that utilizes a thin-film adhesive as described in this embodiment (in this specification, "semiconductor wafer" is used to include the meaning of "semiconductor substrate") is exemplified by having a package having... Figure 2 , Figure 3The process is as shown. First, a semiconductor wafer with at least one semiconductor circuit formed on its surface is prepared (step a). A thin film adhesive is prepared by shaping the adhesive composition (step b). The heating temperature and time for shaping (heat treatment 1) at this time are as described above. The thin film adhesive of the present invention is heat-pressed onto the surface of the prepared semiconductor wafer where the semiconductor circuit is formed, thereby forming an adhesive layer (step c). As for the heat-pressing conditions, the temperature is preferably 50°C or higher and 100°C or lower, more preferably 60°C or higher and 90°C or lower, and even more preferably 65°C or higher and 80°C or lower. The pressure is preferably 0.05 MPa or higher and 2 MPa or lower, more preferably 0.1 MPa or higher and 1.5 MPa or lower, and even more preferably 0.2 MPa or higher and 1 MPa or lower. The pressurization time is preferably 10 seconds or higher and 10 minutes or lower, more preferably 30 seconds or higher and 8 minutes or lower, and even more preferably 1 minute or higher and 6 minutes or lower. In the manufacturing method of this embodiment, a heating step for heat treatment 2 is then included. The temperature in the heating process of heat treatment 2 is preferably 150°C or higher and 210°C or lower, more preferably 160°C or higher and 200°C or lower, and further preferably 170°C or higher and 190°C or lower. The heating time is preferably 30 minutes or higher and 90 minutes or lower, more preferably 40 minutes or higher and 80 minutes or lower, and further preferably 50 minutes or higher and 70 minutes or lower. After the heat pressing and heating processes, a moderately cured resin body is obtained that does not lose the adhesiveness of the adhesive layer and has excellent morphological stability. After stabilizing the morphology of the adhesive layer, the terminals are exposed from the adhesive layer (cured film adhesive 4x), and planarization is performed in a manner that makes the surface of the adhesive layer and the surface of the terminals smoothly coplanar (processes d, d'). Figure 3 In this embodiment, CMP (Chemical Mechanical Planarization) is used to polish the adhesive layer and terminals using a polishing pad 5 to form a flat surface (the planarized adhesive layer 4A and the planarized surface of the terminal 2A). After CMP, the abrasive (slurry) used is washed away. Furthermore, if an adhesive layer suitable for the unevenness of the terminals is formed, steps d and d' can be omitted. Next, two semiconductor wafers with adhesive layers are prepared, and their thin-film adhesive layers are bonded together and multilayered (steps e and f). Figure 2 In this process, a terminal 2B is formed that bonds to the adhesive layer (cured resin body) 4B to be bonded. The bonding temperature at this time, as described at the beginning, is preferably between room temperature (25°C) and 200°C, more preferably room temperature (25°C) or 200°C. At 200°C, this step becomes heat treatment 3. When the bonding temperature is room temperature, the preceding heat treatment 2 step becomes the final heat treatment step before bonding. Through the above steps, a semiconductor package composed of a semiconductor wafer formed by bonding a resin cured body using a thin-film adhesive can be obtained.

[0100] When the joining process is used as a heat treatment process, the temperature is preferably 160°C or higher and 240°C or lower, more preferably 170°C or higher and 230°C or lower, and even more preferably 175°C or higher and 220°C or lower. The pressing force is not particularly limited, but is preferably 2N or higher and 80N or lower, more preferably 4N or higher and 60N or lower, and even more preferably 6N or higher and 50N or lower. The heating time is not particularly limited, but is preferably 1 second or higher and 60 seconds or lower, more preferably 5 seconds or higher and 50 seconds or lower, and even more preferably 7 seconds or higher and 30 seconds or lower.

[0101] The present invention will now be described in more detail with reference to embodiments and comparative examples, but the present invention is not limited to the following embodiments. In particular, Figures 1-6 The illustrated method is merely one example of an embodiment of the present invention and is by no means limited to the illustrated method. Furthermore, in each embodiment and comparative example, the energy storage modulus, loss modulus, loss tangent tanδ evaluation, bonding performance evaluation, and chip shear strength evaluation at the bonding temperature are performed using the methods shown below.

[0102] Example

[0103] (Measurement Example 1)

[0104] <Storage modulus, loss modulus, and loss tangent tanδ at the junction temperature>

[0105] Using the adhesive compositions obtained in the various examples and comparative examples, a single-layer film of adhesive with a length of 300 mm, a width of 200 mm, and a thickness of 200 μm was formed on the release film using a multi-functional coating machine. The cured adhesive film obtained by curing this sample at 180°C for 1 hour was cut into 5 mm × 17 mm (200 μm thickness) pieces, and the release film was peeled off. The storage modulus and loss modulus at each temperature were 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 1 Hz (tensile mode). The storage modulus and loss modulus at each temperature were read. The storage modulus and loss modulus at the bonding temperature were read. The value of the loss tangent tanδ was calculated using the following formula (according to JIS K7244 (formerly K7198:1991)).

[0106] Loss tangent tanδ = Loss modulus ÷ Storage modulus … Number 1

[0107] (Measurement Example 2)

[0108] <Connectivity Assessment>

[0109] First, using a manual laminator (trade name: FM-114, manufactured by TECHNOVISION), at a temperature of 70°C and a pressure of 0.3 MPa, the thin-film adhesive with release film obtained in each example and comparative example was bonded to one side of a dummy silicon wafer (8-inch size, 365 μm thickness). The release film was peeled off from the thin-film adhesive, and then cured in a heated oven at 180°C for 1 hour. For the wafer with thin-film adhesive that underwent this heat treatment, using a manual laminator (trade name: FM-114, manufactured by TECHNOVISION), at room temperature and a pressure of 0.3 MPa, dicing tape (trade name: K-13, manufactured by Furukawa Electric Industries, Ltd.) and a dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were bonded to the side opposite to the dummy silicon wafer. Next, using a cutting device (trade name: DFD-6340, manufactured by DISCO) equipped with dual-axis cutting blades (Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BC), manufactured by DISCO), the dummy silicon wafer is cut from the side to reduce its size to 10mm × 10mm, resulting in a dummy chip with a cured thin film of adhesive (the adhesive thickness is 1.0μm).

[0110] Using the same processing method, the thin film adhesive with a release film obtained in each embodiment and comparative example was cut from the dummy silicon wafer side to make its size 12mm × 12mm, resulting in a dummy chip with a cured thin film adhesive (the adhesive thickness is 1.0μm).

[0111] Next, a 10mm x 10mm dummy chip (test substrate) 12 with a cured thin-film adhesive film attached was removed from the cutting tape using a flip chip bonding machine (trade name: TFC Z100C, manufactured by Shibaura Electric Co., Ltd.). Figure 4 The dummy chip (test substrate) with a 12mm × 12mm diameter and coated with a cured thin-film adhesive is mounted on the stage so that the thin-film adhesive bonds to each other. The mounting conditions are as follows. In addition, when the chuck 11 is heated to 200°C, the stage 14 is also heated to 150°C.

[0112] Chuck 11 temperature: room temperature (25℃) or 200℃

[0113] Stage 14 temperature: room temperature (25℃) or 150℃

[0114] Joint pressure: 40N

[0115] Engagement time: 10 seconds

[0116] For the bonded dummy chips, an ultrasonic flaw detector (SAT) (Hitachi Power Solutions FS300III) was used to observe whether there were gaps at the interface between the cured film adhesives at room temperature (25°C), and the bonding was evaluated according to the following evaluation criteria. In this test, an evaluation grade of "A" is considered acceptable.

[0117] Evaluation benchmark

[0118] AA: No gaps were observed in any of the 100 dummy chips installed.

[0119] A: No gaps were observed in any of the 24 dummy chips installed.

[0120] B: Gaps were observed in more than one but less than three of the 24 installed dummy chips.

[0121] C: Gaps were observed in more than 4 out of the 24 dummy chips installed.

[0122] Furthermore, as an example, what is obtained by observing the joint interface at the cross-section is... Figure 5 The microscopic image shows that the interface between the two thin-film adhesives has disappeared, resulting in a highly bonded state. No voids were observed.

[0123] (Measurement Example 3)

[0124] <Chip Shear Strength Assessment>

[0125] First, using a manual laminator (trade name: FM-114, manufactured by TECHNOVISION), at a temperature of 70°C and a pressure of 0.3 MPa, the thin-film adhesive with release film obtained in each example and comparative example was bonded to one side of a dummy silicon wafer (8-inch size, 365 μm thickness). The release film was peeled off from the thin-film adhesive, and then cured in a heated oven at 180°C for 1 hour. For the wafer with the cured thin-film adhesive, using a manual laminator (trade name: FM-114, manufactured by TECHNOVISION), at room temperature and a pressure of 0.3 MPa, dicing tape (trade name: K-13, manufactured by Furukawa Electric Industries, Ltd.) and a dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were bonded to the side opposite to the dummy silicon wafer. Next, using a cutting device (trade name: DFD-6340, manufactured by DISCO) equipped with dual-axis cutting blades (Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BC), manufactured by DISCO), the dummy silicon wafer was cut from the side to a size of 2mm × 2mm (with an adhesive layer thickness of 1.0μm). The wafer was then subjected to a heat treatment at 180°C for 1 hour to obtain a dummy chip with a cured thin film of adhesive.

[0126] Using the same processing method, the thin film adhesive with release film obtained in each embodiment and comparative example was cut from the dummy silicon wafer side to a size of 12mm × 12mm (the thickness of the adhesive layer is 1.0μm), and a heat treatment of 180°C for 1 hour was performed to obtain a dummy chip with a cured thin film adhesive.

[0127] Next, the 2mm x 2mm dummy chip 12 with thin-film adhesive attached is removed from the cutting tape using a flip chip bonding machine (trade name: TFC Z100C, manufactured by Shibaura Electric Co., Ltd.). Figure 4 However, the width of this dummy chip is narrower than that of the chip shown in the figure. It is mounted on the 12mm × 12mm dummy chip 13 with a cured thin film adhesive placed on the stage so that the thin film adhesive bonds with each other. The mounting conditions at this time are as follows. In addition, when the chuck 11 is heated to 200°C, the stage 14 is also heated to 150°C.

[0128] Chuck 11 temperature: room temperature (25℃) or 200℃

[0129] Stage 14 temperature: room temperature (25℃) or 150℃

[0130] Joint pressure: 10N

[0131] Engagement time: 10 seconds

[0132] The shear strength of the dummy chips bonded with a thin-film adhesive was measured at room temperature (25°C) using an adhesive strength tester (trade name: 4000 universal adhesive strength tester, manufactured by DEJI Co., Ltd.). Specifically, as... Figure 6 As shown, a 2mm × 2mm dummy chip 12 bonded to a 12mm × 12mm dummy chip 13 was used as the object. Using a specified shearing jig 15, the 2mm × 2mm dummy chip 12 was pressed from the side at a height of 10μm from the surface of the adherend at a shearing speed of 0.5mm / sec, and a load was applied. The strength at break was measured at (25°C). The average value of 8 tests was calculated as the chip shear strength. The chip shear strength was evaluated according to the following evaluation criteria. In this test, an evaluation grade of "A" is considered acceptable (according to MIL-STD-883 method number 2019). Furthermore, the chip shear strength is equivalent to the bonding strength in this invention.

[0133] AAA: The average shear strength of the chip is above 40 MPa.

[0134] AA: The average shear strength of the chip is less than 40 MPa and greater than 20 MPa.

[0135] A: The average shear strength of the chip is less than 20MPa and greater than 10MPa.

[0136] B: The average shear strength of the chip is less than 10 MPa and greater than 5 MPa.

[0137] C: The average shear strength of the chip is less than 5 MPa

[0138] (Example 1)

[0139] First, 60 parts by weight of bisphenol A type epoxy resin (trade name: YD-012, weight average molecular weight: 1000, softening point: 81℃, solid, epoxy equivalent: 655, manufactured by Nippon Steel Chemical Materials Co., Ltd.), 140 parts by weight of flexible epoxy resin (trade name: YX-7105, weight average molecular weight: 600, softening point: below 25℃, liquid, epoxy equivalent: 487, manufactured by Mitsubishi Chemical Co., Ltd.), 100 parts by weight of bisphenol A type phenoxy resin (trade name: YP-50, weight average molecular weight: 70000, Tg: 84℃, manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.), and 67 parts by weight of MEK were heated and stirred at 110℃ for 2 hours in a 1000ml separable flask to obtain a resin varnish.

[0140] Next, 367 parts by weight of the resin varnish were transferred to an 800 ml planetary mixer, and 240 parts by weight of silica filler (trade name: SO-C1, average particle size (d50): 0.3 μm, manufactured by Admatechs Co., Ltd.) were added, along with 2.5 parts by weight of imidazole curing agent (trade name: 2PHZ-PW, manufactured by Shikoku Kasei Co., Ltd.) and 3.0 parts by weight of silane coupling agent (trade name: S-510, manufactured by JNC Co., Ltd.). The mixture was stirred and mixed at room temperature for 1 hour, and then vacuum degassing was performed to obtain the mixed varnish (adhesive composition).

[0141] Next, using a multi-functional coating machine (head: doctor blade coating machine, type: MPC-400L, manufactured by Matsuoka Machinery Co., Ltd.), the obtained mixed varnish was applied onto a 38μm thick PET film (release film) after demolding treatment at a processing temperature of 130°C (drying oven 1.5m) and a linear speed of 1.0m / min (dwell time 1.5min). This created a double-layered film (a thin film adhesive with a release film attached) with an adhesive layer having a width of 200mm, a length of 10m, and a thickness of 1μm on the release film. The bonding temperature (clamping temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the aforementioned bonding temperature (200°C).

[0142] (Example 2)

[0143] Except for using 30 parts by weight of bisphenol A type epoxy resin (trade name: YD-012, weight average molecular weight: 1000, softening point: 81°C, solid, epoxy equivalent: 655, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 170 parts by weight of flexible epoxy resin (trade name: YX-7105, weight average molecular weight: 600, softening point: below 25°C, liquid, epoxy equivalent: 487, manufactured by Mitsubishi Chemical Co., Ltd.), the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0144] (Example 3)

[0145] Except for using 0 parts by weight of bisphenol A type epoxy resin (trade name: YD-012, weight average molecular weight: 1000, softening point: 81°C, solid, epoxy equivalent: 655, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 200 parts by weight of flexible epoxy resin (trade name: YX-7105, weight average molecular weight: 600, softening point: below 25°C, liquid, epoxy equivalent: 487, manufactured by Mitsubishi Chemical Co., Ltd.), the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0146] (Example 4)

[0147] Except that 400 parts by weight (of which 100 parts by weight are polyurethane resin) of a polyurethane resin solution (trade name: Dinaleo VA-9310MF, weight average molecular weight: 110,000, Tg: 27°C, room temperature modulus of elasticity: 289 MPa, solvent: MEK / IPA mixed solvent, manufactured by Toyo Chemical Co., Ltd.) was used instead of phenoxy resin, the same procedure as in Example 1 was followed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0148] (Example 5)

[0149] Except that the clamp temperature for bonding evaluation, chip shearing evaluation and the sampling temperature for viscoelastic properties were set to 25°C, the same procedure as in Example 4 was performed to obtain the adhesive composition and the film adhesive.

[0150] (Example 6)

[0151] Except for using 140 parts by weight of the trade name AER9000 (weight average molecular weight: 500, softening point: below 25°C, liquid, epoxy equivalent: 375, manufactured by Asahi Kasei Corporation) instead of YX-7105 as the flexible epoxy resin, the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the aforementioned bonding temperature (200°C).

[0152] (Example 7)

[0153] Except that the clamp temperature for bonding evaluation, chip shearing evaluation, and sampling temperature for viscoelastic properties were set to 25°C, the same procedure as in Example 6 was performed to obtain the adhesive composition and the film adhesive.

[0154] (Example 8)

[0155] Except for using 400 parts by weight of an acrylic polymer solution (trade name: S-2060, mass average molecular weight: 500,000, Tg: -23°C, room temperature (25°C) modulus of elasticity: 50 MPa, solid content 25% (organic solvent: toluene), manufactured by Toa Synthetic Co., Ltd.) instead of phenoxy resin, the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0156] (Example 9)

[0157] Except for the absence of silica filler (trade name: SO-C1, average particle size (d50): 0.3 μm, manufactured by Admatechs Co., Ltd.) and silane coupling agent (trade name: S-510, manufactured by JNC Co., Ltd.), the same procedures as in Example 5 were followed to obtain the adhesive composition and the film adhesive. The clamp temperature for bonding evaluation, chip shearing evaluation, and the sampling temperature for viscoelastic properties were set to 25°C.

[0158] (Example 10)

[0159] Except for using 140 parts by weight of the trade name AER9000 (weight average molecular weight: 500, softening point: below 25°C, liquid, epoxy equivalent: 375, manufactured by Asahi Kasei Corporation) instead of YX-7105 as the flexible epoxy resin, the same procedure was followed as in Example 9 to obtain the adhesive composition and the film adhesive. The clamp temperature for bonding evaluation, chip shearing evaluation, and the sampling temperature for viscoelastic properties were set to 25°C.

[0160] (Comparative Example 1)

[0161] Except for using 140 parts by weight of bisphenol A type epoxy resin (trade name: YD-128, weight average molecular weight: 400, softening point: below 25°C, liquid, epoxy equivalent: 190, manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.) and 840 parts by weight of silica filler (trade name: SO-C1, average particle size (d50): 0.3 μm, manufactured by Admatechs Co., Ltd.) instead of YX-7105, the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0162] (Comparative Example 2)

[0163] Except for using 240 parts by weight of silica filler (trade name: SO-C1, average particle size (d50): 0.3 μm, manufactured by Admatechs Co., Ltd.), the same procedures as in Comparative Example 1 were performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the above bonding temperature (200°C).

[0164] (Comparative Example 3)

[0165] Except for the absence of silica filler (trade name: SO-C1, average particle size (d50): 0.3 μm, manufactured by Admatechs Co., Ltd.), the same procedures as in Comparative Example 1 were performed to obtain the adhesive composition and the film adhesive. The bonding temperature (clamp temperature) for bonding performance evaluation and chip shearing evaluation was set to 200°C. The sampling temperature for viscoelastic properties was also set to the aforementioned bonding temperature (200°C).

[0166] (Comparative Example 4)

[0167] Except for using 150 parts by weight of bisphenol A type epoxy resin (trade name: YD-012, weight average molecular weight: 1000, softening point: 81°C, solid, epoxy equivalent: 655, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 50 parts by weight of flexible epoxy resin (trade name: YX-7105, weight average molecular weight: 600, softening point: below 25°C, liquid, epoxy equivalent: 487, manufactured by Mitsubishi Chemical Co., Ltd.), the same procedure as in Example 1 was performed to obtain the adhesive composition and the film adhesive. The clamp temperature for bonding evaluation, chip shearing evaluation, and the sampling temperature for viscoelastic properties were set to 25°C.

[0168] Table 2

[0169]

[0170] Table 3

[0171]

[0172] (Inspection)

[0173] The adhesive compositions used in the examples all employed epoxy resins with an epoxy equivalent of 300 g / eq or higher. As film-forming properties, they satisfied the following: a storage modulus of 2000 MPa or less at the bonding temperature (25°C, 200°C) and a loss tangent of 0.03 or higher at the bonding temperature. As a result, excellent results (A, AA, AAA) were achieved in terms of bonding performance evaluation and chip shear strength.

[0174] In contrast, in the adhesive compositions of Comparative Examples 1-3, the epoxy equivalent of the epoxy resin was 189, which is far below 300, failing to meet the requirements of a film storage modulus of 2000 MPa or less and a loss tangent of 0.03 or more. As a result, insufficient results were obtained in terms of bonding evaluation and chip shear strength (B, C).

[0175] Examples 4 and 5, as well as Examples 6 and 7, are compositions formulated in the same way. However, regardless of whether the bonding temperature is 200°C or 25°C, they can meet the energy storage modulus and loss tangent values ​​of the present invention. They can also perform well at the bonding temperature, whether at low temperature or heated temperature.

[0176] In the adhesive compositions of the examples, solid epoxy resin and liquid epoxy resin are mixed. Only Example 3 is an example containing only liquid epoxy resin, but it showed good results in both bonding evaluation and chip shearing. However, as mentioned above, the presence of only liquid epoxy resin results in excessive viscosity and poor handling performance.

[0177] Various polymers, such as BisA-type phenoxy resins, polyurethane resins, and acrylic resins, can be used as polymers constituting the adhesive composition. However, Example 8, which uses acrylic resin, achieved an A grade in both bonding evaluation and chip shear strength, which is inferior to the other examples. From this perspective, phenoxy resins and polyurethane resins are preferred as polymers constituting the matrix framework.

[0178] Furthermore, in the adhesive compositions of the embodiments, except for Example 3, the liquid epoxy resin was more abundant than the solid epoxy resin. Conversely, if the solid epoxy resin were more abundant, it would result in poorer results in terms of bonding performance and chip shear strength, as in Comparative Example 4.

[0179] Explanation of reference numerals in the attached figures:

[0180] 1. Silicon substrate

[0181] 2 copper terminals

[0182] 2A Flattened Copper Terminals

[0183] 2B-connected copper terminals

[0184] 4. Film-like adhesives

[0185] 4A Planarized film adhesive

[0186] 4B bonding film adhesive

[0187] 4x Curing film adhesive

[0188] 5. Grinding pad

[0189] 11 Chucks

[0190] 12, 13 Test substrates

[0191] 14 platforms

[0192] 15. Cutting clamp

Claims

1. An adhesive composition comprising at least an epoxy resin (A), an epoxy resin curing agent (B), and a polymeric component (C), characterized in that, The storage modulus after curing is 2000 MPa or less, and the loss tangent is 0.03 or more under the following conditions. The bond strength of the cured compositions when bonded together under the following conditions is 5 MPa or more. [The storage modulus and loss tangent after curing were measured by heat curing the adhesive composition at 180°C for 1 hour to form a 5mm×17mm×200μm film-like adhesive sheet. The measurement was performed at a temperature range of 20–300°C, a heating rate of 5°C / min, and a frequency of 1Hz. The measured values ​​at the following bonding temperatures were sampled.] [Joint temperature: any temperature above 25°C and below 300°C], [The bonding strength is the strength of two chips with a 1.0 μm thick thin film adhesive bonded together at a bonding temperature and then peeled off at room temperature. The thin film adhesive is made by heating the adhesive composition at 180°C for 1 hour to thermally cure it.] 2. The adhesive composition according to claim 1, characterized in that, The epoxy resin (A) used in the adhesive composition has an epoxy equivalent of 300 g / eq or more, and the content of the epoxy resin (A) is 20% by mass or more of the total amount of epoxy resin (A), epoxy resin curing agent (B), and polymer component (C).

3. The adhesive composition according to claim 1, characterized in that, The epoxy resin (A) is formed by mixing liquid epoxy resin and solid epoxy resin at room temperature. When the polymer component (C) is set to 100 parts by mass, the content of the liquid epoxy resin is 100 to 250 parts by mass, the content of the solid epoxy resin is 15 to 90 parts by mass, and the mass ratio of the solid epoxy resin to the liquid epoxy resin is in the range of 1:10 to 6:

10.

4. The adhesive composition according to claim 1, characterized in that, The epoxy resin curing agent (B) is an imidazole curing agent.

5. The adhesive composition according to claim 1, characterized in that, The bonding temperature is above 25°C and below 200°C.

6. A film-like adhesive, characterized in that, It is formed by heat treatment of the adhesive composition according to any one of claims 1 to 5.

7. The film-like adhesive according to claim 6, characterized in that, The thickness ranges from 0.1 to 50 μm.

8. A method for manufacturing a semiconductor package, characterized in that, An adhesive layer is formed by bonding and thermally curing the thin-film adhesive of claim 6 onto a semiconductor wafer on which at least one semiconductor circuit is formed. The semiconductor wafer is then bonded and stacked through the adhesive layer. The bonding is achieved by using a resin-cured body formed by directly pressing the adhesive layer at room temperature or by pressing it after further thermal curing, thereby multiplying the semiconductor wafer.

9. The method for manufacturing a semiconductor package according to claim 8, characterized in that, The process includes the following steps: The terminals are exposed from the adhesive layer, and the adhesive layer is planarized so that the surface of the adhesive layer is coplanar with the surface of the terminals.

10. A semiconductor package, characterized in that, It is composed of a semiconductor wafer formed by bonding a resin cured body using the thin-film adhesive as described in claim 6.

11. A film-like adhesive, formed by heat-treating an adhesive composition containing epoxy resin (A), epoxy resin curing agent (B), and polymeric component (C), characterized in that, The energy storage modulus is below 2000 MPa and the loss tangent is above 0.03 under the following conditions, and the bonding strength is above 5 MPa under the following conditions during bonding. [The storage modulus and loss tangent were measured on a 5mm × 17mm × 200μm thin film adhesive sheet under the following conditions: a temperature range of 20–300℃, a heating rate of 5℃ / min, and a frequency of 1Hz. The measured values ​​at the following bonding temperatures were sampled.] [Joint temperature: any temperature above 25°C and below 300°C], [The bonding strength is the strength of two chips coated with a 1.0 μm thick thin film adhesive, bonded together at the bonding temperature, when peeled off at room temperature.]

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