Adhesive for semiconductors, and, semiconductor device and method of manufacturing the same

Abstract

A semiconductor adhesive comprising a thermoplastic resin, a thermosetting resin, a curing agent, and an organic acid, wherein the organic acid is a compound having two or more acidic functional groups and an acid dissociation constant pKa of 4.0 or less.

Description

Technology Field

[0001] The present disclosure relates to an adhesive for semiconductors, and a semiconductor device and a method for manufacturing the same. Background Technology

[0002] Conventionally, wire bonding methods using fine metal wires, such as gold wires, have been widely applied to connect semiconductor chips and substrates.

[0003] Recently, in order to meet the demands for high functionality, high integration, and high speed for semiconductor devices, the flip-chip connection method (FC connection method), which directly connects a semiconductor chip and a substrate by forming conductive protrusions called bumps on the semiconductor chip or substrate, is becoming widespread.

[0004] For example, regarding the connection between a semiconductor chip and a substrate, the COB (Chip On Board) type connection method, which is actively used in BGA (Ball Grid Array) and CSP (Chip Size Package), also corresponds to the FC connection method. In addition, the FC connection method is also widely used as a COC (Chip On Chip) type connection method, which connects semiconductor chips by forming a connection portion (bump or wiring) on ​​a semiconductor chip, and a COW (Chip On Wafer) type connection method, which connects semiconductor chips and semiconductor wafers by forming a connection portion (bump or wiring) on ​​a semiconductor wafer (for example, see Patent Document 1).

[0005] In addition, for packages where further miniaturization, thinning, and high functionality are strongly required, chip stacked packages, POP (Package On Package), and TSV (Through-Silicon Via), which utilize the aforementioned connection methods in a stacked and multi-layered manner, are also beginning to be widely adopted. Since such stacking and multi-layering technologies arrange semiconductor chips in three dimensions, they allow for smaller packages compared to methods that arrange them in two dimensions. Furthermore, stacking and multi-layering technologies are attracting attention as next-generation semiconductor wiring technologies because they are effective in improving semiconductor performance, reducing noise, decreasing mounting area, and saving power. Prior art literature

[0006] Patent Document 1: Japanese Published Patent Application No. 2008-294382 The problem to be solved

[0007] Recently, from the perspective of improving productivity, a process has been proposed in which multiple semiconductor chips are mounted on a mounting member (semiconductor chip, semiconductor wafer, wiring circuit board, etc.) and temporarily fixed using a semiconductor adhesive, and then cured and sealed in batches or in separate steps. In this process, the semiconductor chips are temporarily fixed on the mounting member by applying heat (approximately 60 to 155°C) to a stage such that the semiconductor adhesive can flow, and then the semiconductor adhesive is cured in batches or in separate steps by reflow or main compression at a temperature above the melting point of the connection part (e.g., approximately 260°C). According to this process, multiple packages can be manufactured efficiently.

[0008] In the above process, since semiconductor chips are mounted sequentially, thermal history by the stage is continuously applied to the initially mounted semiconductor chips and semiconductor adhesives until the mounting of the last semiconductor chip is completed. Consequently, as the number of semiconductor chips increases, the curing of the semiconductor adhesive used to temporarily fix the initially mounted chips proceeds only partially, and voids tend to remain unremoved due to the pressure applied during batch curing. To improve this problem, the semiconductor adhesive is required to possess excellent thermal history resistance; that is, it must be capable of suppressing the progression of the curing reaction caused by thermal history during temporary fixation.

[0009] Accordingly, the present disclosure aims to provide a semiconductor adhesive capable of reducing the reaction rate after thermal history. Furthermore, the present disclosure aims to provide a semiconductor device using the said semiconductor adhesive and a method for manufacturing the same. means of solving the problem

[0010] To achieve the above objective, the present disclosure provides a semiconductor adhesive comprising a thermoplastic resin, a thermosetting resin, a curing agent, and an organic acid, wherein the organic acid is a compound having two or more acidic functional groups and an acid dissociation constant pKa of 4.0 or less.

[0011] The above organic acid has two or more acidic functional groups and has an acid dissociation constant pKa of 4.0 or less, so it can form a strong salt with at least a portion of the curing agent. Furthermore, by forming a salt between the curing agent and the organic acid, the reaction between the curing agent and the thermosetting resin can be inhibited. Therefore, according to the semiconductor adhesive containing the above organic acid, the curing reaction between the curing agent and the thermosetting resin can be suppressed by the thermal history during temporary fixing, and the reaction rate after thermal history can be reduced. In addition, during the main compression, heat at a temperature higher than the thermal history by the stage during temporary fixing is applied, thereby separating the curing agent and the organic acid that had formed the salt. As a result, during the main compression, the separated curing agent reacts with the thermosetting resin, thereby obtaining a semiconductor device in which the retention of voids is suppressed.

[0012] The acidic functional group may include at least one group selected from the group consisting of carboxyl groups, sulfoxyl groups, and phosphate groups. The acidic functional group is not particularly limited as long as it is an acidic functional group capable of forming a salt with a basic functional group included in the curing agent, and the organic acid may include multiple acidic functional groups.

[0013] The equivalent ratio of the acidic functional group included in the organic acid to the basic functional group included in the curing agent may be 1.0 or higher. By having the said equivalent ratio of 1.0 or higher, the amount of curing agent that is not reacting with the organic acid before the main pressing is reduced, and the reaction rate after thermal history can be reduced compared to when the said equivalent ratio is less than 1.0.

[0014] The above organic acid may include a compound represented by the following general formulas (1-1), (1-2), or (1-3).

[0015] [Chemical Formula 1]

[0016]

[0017] [Chemical Formula 2]

[0018]

[0019] [Chemical Formula 3]

[0020]

[0021] [Equations (1-1), (1-2) and (1-3), R 1 represents an electronic absorbing device, and R 2 represents a hydrogen atom or an electron-withdrawing group, and R 3 represents a hydrogen atom or a monovalent organic group, X represents an oxygen atom or a sulfur atom, and n 1 represents an integer from 0 to 15, and n 2 and n 3 are respectively, n 2 +n 3 This represents an integer greater than or equal to 1 selected to be an integer between 2 and 15, where m represents 1 or 2. Additionally, there are multiple R 3 They may be identical or different.

[0022] The melting point of the above organic acid may be 50 to 250°C. Since such an organic acid sufficiently exhibits flux activity before the curing reaction between the thermosetting resin and the curing agent occurs, a semiconductor device with even better connection reliability can be realized using a semiconductor adhesive containing said organic acid.

[0023] The above-mentioned curing agent may include an amine-based curing agent. Such a compound can exhibit excellent curing characteristics through the curing reaction between the thermosetting resin and the curing agent, thereby further improving the reflow resistance of the semiconductor device.

[0024] The above curing agent may include an imidazole-based curing agent. By using such a compound, the stability of the semiconductor adhesive can be further improved.

[0025] The structure of the above-mentioned imidazole-based curing agent may include a triazine ring. By using such a compound, the stability of the semiconductor adhesive can be further improved.

[0026] The present disclosure further provides a semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, comprising a method for manufacturing a semiconductor device comprising a sealing process in which the semiconductor adhesive of the present disclosure is cured by applying heat under atmospheric pressure or a pressurized atmosphere, and at least a portion of the connection portion is sealed by the cured semiconductor adhesive.

[0027] The above manufacturing method may further comprise a process of placing a plurality of semiconductor chips on a stage before the sealing process, and a process of heating the stage to 60 to 155°C, sequentially placing another semiconductor chip on each of the plurality of semiconductor chips placed on the stage with the semiconductor adhesive interposed therebetween, and obtaining a plurality of laminates formed by stacking the semiconductor chip, the semiconductor adhesive, and the other semiconductor chip in this order.

[0028] Alternatively, the above manufacturing method may further comprise a process of placing a wiring circuit board or a semiconductor wafer on a stage before the sealing process, and a process of heating the stage to 60 to 155°C while sequentially placing a plurality of semiconductor chips on the wiring circuit board or semiconductor wafer placed on the stage with the semiconductor adhesive interposed therebetween, and obtaining a laminate formed by stacking the wiring circuit board, the semiconductor adhesive, and the plurality of semiconductor chips in this order, or a laminate formed by stacking the semiconductor wafer, the semiconductor adhesive, and the plurality of semiconductor chips in this order.

[0029] The present disclosure further provides a semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, wherein at least a portion of the connection portion is sealed by a cured product of the semiconductor adhesive of the present disclosure, which is cured by applying heat under atmospheric pressure or a pressurized atmosphere. Effects of the invention

[0030] According to the present disclosure, in a process of temporarily fixing a plurality of semiconductor chips onto a mounting member by interposing a semiconductor adhesive and performing curing and sealing in batches, voids that may remain in the semiconductor adhesive can be reduced. According to the present disclosure, a semiconductor adhesive that enables the reduction of such voids and the fabrication of a semiconductor device with excellent connectivity, and a semiconductor device using said semiconductor adhesive and a method for manufacturing the same can be provided. Brief explanation of the drawing

[0031] FIG. 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device. FIG. 2 is a schematic cross-sectional view showing one embodiment of a semiconductor device. FIG. 3 is a schematic cross-sectional view showing one embodiment of a semiconductor device. Figure 4 is a circuit diagram of a semiconductor chip used to evaluate connectivity. Specific details for implementing the invention

[0032] Hereinafter, an embodiment of the present disclosure will be described in detail with reference to the drawings as appropriate. In addition, identical or substantial parts in the drawings are denoted by the same reference numerals, and redundant descriptions are omitted. Furthermore, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specifically stated. Also, the dimensional ratios in the drawings are not limited to the ratios shown.

[0033] The upper and lower limits of the numerical ranges described in this specification may be combined arbitrarily. The numerical values ​​described in the examples may also be used as the upper or lower limits of the numerical range. In this specification, "(meth)acrylic" means acrylic or the corresponding methacrylic.

[0034] <Adhesive for Semiconductors and Method for Manufacturing the Same>

[0035] The semiconductor adhesive of the present embodiment contains a thermoplastic resin (hereinafter referred to as "component (a)" in some cases), a thermosetting resin (hereinafter referred to as "component (b)" in some cases), a curing agent (hereinafter referred to as "component (c)" in some cases), and an organic acid (hereinafter referred to as "component (d)" in some cases). The semiconductor adhesive of the present embodiment may also contain a filler (hereinafter referred to as "component (e)" in some cases) as needed.

[0036] The heat generation amount of the DSC curve obtained by differential scanning calorimetry (DSC) of the semiconductor adhesive of the present embodiment at 60 to 155°C may be 20 J / g or less. Here, differential scanning calorimetry is performed by heating the semiconductor adhesive in an air or nitrogen atmosphere with a weight of 10 mg of the semiconductor adhesive sample, a measurement temperature range of 30 to 300°C, and a heating rate of 10°C / min. The heat generation amount is calculated by integrating the peak area.

[0037] Conventional semiconductor adhesives have an exothermic peak in the temperature range of 60 to 155°C on the DSC curve. It is presumed that the exothermic reaction in this temperature range originates from the reaction between the thermosetting resin and the organic acid in the semiconductor adhesive, and it is presumed that if this reaction proceeds, the semiconductor adhesive partially hardens, and its fluidity decreases. Meanwhile, the temporary fixation of semiconductor chips using semiconductor adhesives is typically performed by heating the semiconductor adhesive to, for example, 60 to 155°C and making it flow appropriately. Therefore, in a process in which multiple semiconductor chips are mounted on a substrate (semiconductor chip, semiconductor wafer, wiring circuit board, etc.) via a semiconductor adhesive and then cured and sealed collectively under pressure conditions, if a conventional semiconductor adhesive is used, it is presumed that when the semiconductor chips are temporarily fixed, the thermosetting resin and the organic acid in the semiconductor adhesive react, causing the curing of the semiconductor adhesive to proceed partially, and thus it may not flow sufficiently during collective curing under pressure conditions. Meanwhile, in the semiconductor adhesive of the present embodiment, if the heat generation amount of the DSC curve at 60 to 155°C is 20 J / g or less, it is difficult for curing to proceed in the temperature range (e.g., 60 to 155°C) where the semiconductor chip is temporarily fixed. Therefore, by using a semiconductor adhesive that satisfies the heat generation condition in the above process, it is possible to temporarily fix multiple semiconductor chips while maintaining sufficient fluidity of the semiconductor adhesive, and to reduce the occurrence of voids during batch curing. Furthermore, as a result of the reduction in void occurrence, it is expected that defects (such as peeling of the semiconductor adhesive or electrical connection failure at the connection part) are less likely to occur even if the connection part is heated to a temperature above the melting point (e.g., 260°C) during the reflow process. In other words, according to the semiconductor adhesive that satisfies the heat generation condition, there is a tendency to improve reflow reliability (down-reflowability) in the manufacture of semiconductor devices.

[0038] From the perspective of facilitating the achievement of the effects of the present invention, the heat generation amount of the above DSC curve from 60 to 155°C is preferably 15 J / g or less, more preferably 10 J / g or less, and more preferably 5 J / g or less. From the perspective of facilitating the achievement of the effects of the present invention, the heat generation amount of the above DSC curve from 60 to 155°C may be 20% or less, 15% or less, or 10% or less of the heat generation amount from 60 to 280°C. From the perspective of facilitating the achievement of the effects of the present invention, the heat generation amount of the above DSC curve from 60 to 280°C may be 50 J / g or more or 100 J / g or more, 200 J / g or less or 180 J / g or less, or 50 to 200 J / g, 100 to 200 J / g, or 100 to 180 J / g. In order to easily obtain the effects of the present invention, it is preferable that the above DSC curve does not have an exothermic peak at an onset temperature of 155°C or lower.

[0039] Hereinafter, each component constituting the semiconductor adhesive of the present embodiment will be described.

[0040] (a) Thermoplastic resin

[0041] (a) As for the components, although not particularly limited, examples include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, uretane resin, and acrylic rubber. Among these, phenoxy resin, polyimide resin, acrylic resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin are preferred from the perspective of excellent heat resistance and film-forming properties, and phenoxy resin, polyimide resin, and acrylic resin are more preferred. These (a) components may be used alone, or may be used as a mixture or copolymer of two or more types.

[0042] The weight average molecular weight (Mw) of component (a) is preferably 10,000 or more, more preferably 40,000 or more, and more preferably 60,000 or more. With such component (a), film formability and heat resistance of the adhesive can be further improved. Also, if the weight average molecular weight is 10,000 or more, it is easy to impart flexibility to the semiconductor adhesive on the film, so it is easy to obtain even better processability. Also, the weight average molecular weight of component (a) is preferably 1,000,000 or less, and more preferably 500,000 or less. With such component (a), the viscosity of the film is reduced, so the embedding ability for bumps is improved, and mounting can be done even more without voids. In these regards, the weight average molecular weight of (a) component is preferably 10,000 to 1,000,000, more preferably 40,000 to 500,000, and more preferably 60,000 to 500,000.

[0043] In addition, in this specification, the weight-average molecular weight refers to the weight-average molecular weight in polystyrene equivalent, measured using GPC (Gel Permeation Chromatography). An example of the measurement conditions for the GPC method is shown below.

[0044] Device: HCL-8320GPC, UV-8320 (Product name, manufactured by Tosho Co., Ltd.), or HPLC-8020 (Product name, manufactured by Tosho Co., Ltd.)

[0045] Column: TSKgel superMultiporeHZ-M×2, or 2 pieces of GMHXL+1 piece of G-2000XL

[0046] Detector: RI or UV detector

[0047] Column temperature: 25~40℃

[0048] Eluent: Select a solvent in which the polymer component dissolves. Examples of solvents include THF (tetrahydrofuran), DMF (N,N-dimethylformamide), DMA (N,N-dimethylacetamide), NMP (N-methylpyrrolidone), and toluene. Additionally, if a polar solvent is selected, the concentration of phosphoric acid may be adjusted to 0.05 to 0.1 mol / L (typically 0.06 mol / L) and the concentration of LiBr to 0.5 to 1.0 mol / L (typically 0.63 mol / L).

[0049] Flow rate: 0.30~1.5 mL / min

[0050] Standard material: Polystyrene

[0051] (a) Content of component C a Content of component (b) for C b Of C b / C a (Mass ratio) is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, preferably 5 or less, more preferably 4.5 or less, and even more preferably 4 or less. Ratio C b / C a By making 0.01 or higher, better curability and adhesion are obtained, and non-C b / C a Better film formation properties are obtained by making 5 or less. In these regard, non-C b / C a It is preferable that it be 0.01 to 5, more preferable that it be 0.1 to 4.5, and even more preferable that it be 1 to 4.

[0052] The glass transition temperature of component (a) is preferably -50°C or higher, more preferably -40°C or higher, and even more preferably -30°C or higher, from the perspective of improving connection reliability, etc., and is preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 180°C or lower, from the perspective of laminating properties, etc. The glass transition temperature of component (a) is preferably -50 to 220°C, more preferably -40 to 200°C, and even more preferably -30 to 180°C. According to a semiconductor adhesive containing such component (a), the amount of wafer warping can be further reduced during the wafer-level mounting process, and the heat resistance and film-forming properties of the semiconductor adhesive can be further improved. The glass transition temperature of component (a) can be measured by differential scanning calorimetry (DSC).

[0053] The content of component (a) is preferably 30 mass% or less based on the total solid content of the semiconductor adhesive, more preferably 25 mass% or less, and even more preferably 20 mass% or less. If the content of component (a) is 30 mass% or less, the semiconductor adhesive can obtain good reliability during temperature cycle testing and can obtain good adhesion at a reflow temperature of around 260°C even after moisture absorption. In addition, the content of component (a) is preferably 1 mass% or more based on the total solid content of the semiconductor adhesive, more preferably 3 mass% or more, and even more preferably 5 mass% or more. If the content of component (a) is 1 mass% or more, the amount of wafer warping can be further reduced during the wafer-level mounting process, and the heat resistance and film-forming ability of the semiconductor adhesive can be further improved. In addition, if the content of component (a) is 5 mass% or more, the occurrence of burrs and damage during external processing into a wafer shape can be suppressed. The content of component (a) is preferably 1 to 30 mass% based on the total solid content of the semiconductor adhesive, more preferably 3 to 30 mass%, and more preferably 5 to 30 mass%, from the above perspective and from the perspective that it is easy to impart flexibility to the semiconductor adhesive on a film and thus obtain even better processability. In addition, "total solid content of the semiconductor adhesive" is the amount excluding the amount of solvent contained in the semiconductor adhesive from the total amount of the semiconductor adhesive. In this specification, "total solid content of the semiconductor adhesive" may be referred to as "total amount of components (a) to (e)."

[0054] (b) thermosetting resin

[0055] (b) As for the component, any component having two or more reactive groups within the molecule can be used without particular limitation. Since the semiconductor adhesive contains a thermosetting resin, the adhesive can be cured by heating, and the cured adhesive exhibits high heat resistance and adhesion to the chip, thereby obtaining excellent downflow properties.

[0056] (b) As components, examples include epoxy resin, phenolic resin, imide resin, urea resin, melamine resin, silicone resin, (meth)acrylic compound, and vinyl compound. Among these, epoxy resin, phenolic resin, and imide resin are preferred from the perspective of excellent heat resistance (reflow resistance) and storage stability, epoxy resin and imide resin are more preferred, and epoxy resin is more preferred. These (b) components may be used alone or as a mixture or copolymer of two or more types. Among conventional semiconductor adhesives, particularly when the thermosetting resin is epoxy resin, melamine resin, or urea resin, a reaction with the organic acid described below is likely to proceed in the temperature range of 60 to 155°C, and partial curing tends to proceed before batch curing; however, in the present embodiment, even if the thermosetting resin includes at least one resin selected from the group consisting of epoxy resin, melamine resin, and urea resin, such a reaction and partial curing are difficult to occur.

[0057] As epoxy resins and imide resins, examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin and various polyfunctional epoxy resins, nadimide resin, allylinadimide resin, maleimide resin, amideimide resin, imide acrylate resin, various polyfunctional imide resins and various polyimide resins. These may be used alone or as a mixture of two or more types.

[0058] (b) In order to suppress the decomposition and volatile components that occur when connecting at high temperatures, it is preferable to use a component in which the thermal weight loss rate at 250°C is 5% or less when the temperature at the time of connection is 250°C, and in which the thermal weight loss rate at 300°C is 5% or less when the temperature at the time of connection is 300°C.

[0059] (b) The content of the component is, for example, 5 mass% or more, preferably 15 mass% or more, and more preferably 30 mass% or more, based on the total solid content of the semiconductor adhesive. (b) The content of the component is, for example, 80 mass% or less, preferably 70 mass% or less, and more preferably 60 mass% or less, based on the total solid content of the semiconductor adhesive. (b) The content of the component is, for example, 5 to 80 mass%, preferably 15 to 70 mass%, and more preferably 30 to 60 mass%, based on the total solid content of the semiconductor adhesive.

[0060] (c) Curing agent

[0061] (c) The component may be a curing agent capable of forming a salt with an organic acid described below. Examples of components (c) include amine-based curing agents (amines) and imidazole-based curing agents (imidazoles). If component (c) includes an amine-based curing agent or an imidazole-based curing agent, it exhibits flux activity that suppresses the formation of an oxide film at the connection site, thereby improving connection reliability and insulation reliability. Furthermore, if component (c) includes an amine-based curing agent or an imidazole-based curing agent, storage stability is further improved, and there is a tendency for decomposition or deterioration due to moisture absorption to occur. Additionally, if component (c) includes an amine-based curing agent or an imidazole-based curing agent, the curing speed can be easily adjusted, and the rapid curing property makes it easier to realize short-time connections aimed at improving productivity.

[0062] Each curing agent is described below.

[0063] (i) Amine-based curing agent

[0064] As an amine-based curing agent, for example, dicyandiamide can be used.

[0065] The content of the amine-based curing agent is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the above-mentioned component (b). In addition, the content of the amine-based curing agent is preferably 10 parts by mass or less with respect to 100 parts by mass of the above-mentioned component (b), and more preferably 5 parts by mass or less. If the content of the amine-based curing agent is 0.1 parts by mass or more, the curability tends to improve, and if it is 10 parts by mass or less, the semiconductor adhesive does not cure before the metal bond is formed, so there is a tendency for connection defects to occur. From these perspectives, the content of the amine-based curing agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned component (b), and more preferably 0.1 to 5 parts by mass.

[0066] (ii) Imidazole-based curing agent

[0067] As imidazole-based curing agents, for example, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazoleyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazoleyl-(1')]-ethyl-s-triazine, Examples include 2,4-diamino-6-[2'-ethyl-4'-methylimidazoleyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoleyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and imidazoles. Among these, in terms of excellent curability, storage stability, and connection reliability, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazoleyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazoleyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoleyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred. These may be used alone or in combination of two or more. Additionally, these may be used as latent curing agents in the form of microencapsulations.

[0068] The content of the imidazole-based curing agent is preferably 0.1 parts by mass or more per 100 parts by mass of component (b). Furthermore, the content of the imidazole-based curing agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2.3 parts by mass or less per 100 parts by mass of component (b). When the content of the imidazole-based curing agent is 0.1 parts by mass or more, the curability tends to improve. If the content of the imidazole-based curing agent is 10 parts by mass or less, the semiconductor adhesive does not cure before the metal bond is formed, making it difficult for connection defects to occur, and also making it easier to suppress the occurrence of voids in the curing process under a pressurized atmosphere. From these perspectives, the content of the imidazole-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 2.3 parts by mass per 100 parts by mass of component (b).

[0069] (c) Each component may be used individually or as a mixture of two or more types. For example, an imidazole-based curing agent may be used alone or together with an amine-based curing agent. As for component (c), other curing agents that function as curing agents for component (b) may also be used.

[0070] The content of component (c) is preferably 0.5 parts by mass or more per 100 parts by mass of component (b). Also, the content of component (c) is preferably 20 parts by mass or less, more preferably 6 parts by mass or less, and even more preferably 4 parts by mass or less per 100 parts by mass of component (b). When the content of component (c) is 0.5 parts by mass or more, there is a tendency for sufficient curing to proceed. When the content of component (c) is 20 parts by mass or less, there is a tendency to suppress the rapid progression of curing and the increase in reaction sites, and to prevent a decrease in reliability due to shortened molecular chains or residual unreacted groups, and also to suppress the presence of voids when curing under a pressurized atmosphere. In these regard, the content of component (c) is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of component (b), more preferably 0.5 to 6 parts by mass, and more preferably 0.5 to 4 parts by mass.

[0071] The content of component (c) is preferably 0.5 mass% or more based on the total solid content of the semiconductor adhesive. In addition, the content of component (c) is preferably 2.3 mass% or less, more preferably 2.0 mass% or less, and even more preferably 1.5 mass% or less based on the total solid content of the semiconductor adhesive. When the content of component (c) is 0.5 mass% or more, there is a tendency for sufficient curing to proceed. When the content of component (c) is 2.3 mass% or less, there is a tendency to suppress the rapid progression of curing and the increase in reaction sites, and to prevent a decrease in reliability caused by shortening of molecular chains or the presence of unreacted groups, and also to suppress the presence of voids when curing under a pressurized atmosphere. In these regards, the content of component (c) is preferably 0.5 to 2.3 mass% based on the total solid content of the semiconductor adhesive, more preferably 0.5 to 2.0 mass%, and even more preferably 0.5 to 1.5 mass%.

[0072] When a semiconductor adhesive includes an amine-based curing agent as a component (c), excellent curing characteristics are exhibited through a curing reaction with an epoxy resin, thereby further improving the downflowability of the semiconductor device.

[0073] (d) organic acid

[0074] (d) The component is an organic acid. Since the semiconductor adhesive includes component (d), the oxide film of the metal at the connection point and the coating resulting from OSP treatment can be removed, making it easy to obtain excellent connection reliability.

[0075] (d) The component has two or more acidic functional groups. Also, the acid dissociation constant pKa of the component (d) is 4.0 or less. By having two or more acidic functional groups and an acid dissociation constant pKa of 4.0 or less, the semiconductor adhesive can reduce the reaction rate after thermal history caused by thermal history during temporary fixation.

[0076] (d) Since the component has two or more acidic functional groups, it may have multiple acid dissociation constants. An acid dissociation constant pKa of 4.0 or less indicates that at least one of the multiple acid dissociation constants must be 4.0 or less.

[0077] The acid dissociation constant pKa of component (d) is 4.0 or less, preferably 3.5 or less, more preferably 2.5 or less. Also, the acid dissociation constant pKa of component (d) is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. By having the acid dissociation constant pKa of component (d) be 4.0 or less, a stronger salt is formed with the basic functional group, thereby suppressing the reaction with the epoxy resin.

[0078] (d) The component may include at least one group selected from the group consisting of a carboxyl group, a sulfoxyl group, and a phosphate group as an acidic functional group. The acidic functional group is not particularly limited as long as it is an acidic functional group capable of forming a salt with a basic functional group included in the curing agent. Since the component (d) is a compound having a carboxyl group (e.g., a carboxylic acid), it is easier to obtain even better connection reliability. From the view that the effects of the present invention are easier to obtain because the component (d) is a compound having a carboxyl group (e.g., a carboxylic acid), it is preferable that the component (b) is at least one thermosetting resin selected from the group consisting of epoxy resin, uretain resin, and urea resin, and the component (c) is at least one curing agent selected from the group consisting of an amine-based curing agent and an imidazole-based curing agent. In addition, the component (d) may further have an acid group other than a carboxyl group, a sulfoxyl group, or a phosphate group.

[0079] (d) The component may be a compound having a structure represented by the following general formulas (1-1), (1-2) or (1-3).

[0080] [Chemical Formula 4]

[0081]

[0082] [Chemical Formula 5]

[0083]

[0084] [Chemical Formula 6]

[0085]

[0086] Among equations (1-1) to (1-3), R 1 represents an electronic absorbing device, and R 2 represents a hydrogen atom or an electron-withdrawing group, and R 3 represents a hydrogen atom or a monovalent organic group, X represents an oxygen atom or a sulfur atom, and n 1 represents an integer from 0 to 15, and n 2 and n3 are respectively, n 2 +n 3 This represents an integer greater than or equal to 1 selected to be an integer between 2 and 15, where m represents 1 or 2. Additionally, there are multiple R 3 They may be identical or different.

[0087] Examples of electron-withdrawing groups include sulfonyl groups, nitro groups, cyano groups, halogen groups, and carbonyl groups. (d) The component may have two or more electron-withdrawing groups. Also, the α-carbon of the acidic functional group in the component (d) may constitute part of the electron-withdrawing group. For example, in the above formula (1-2), the α-carbon of the acidic functional group becomes part of the carbonyl group. That is, the component (d) can be said to have a structure in which the electron-withdrawing group is directly bonded to the α-carbon of the acidic functional group, or a structure in which the α-carbon of the acidic functional group constitutes part of the electron-withdrawing group. From the perspective of easily obtaining excellent flux activity and easily obtaining the effects of the present invention, it is preferable that the electron-withdrawing group includes at least one selected from the group consisting of cyano groups, halogen groups, and carbonyl groups, and it is more preferable that it include a carbonyl group.

[0088] (d) The component is preferably a compound having 1 to 3 acidic functional groups, and more preferably a compound having 1 to 3 carboxyl groups as acidic functional groups. (d) The component is preferably to include at least one selected from the group consisting of monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. When using the component (d) having 1 to 3 carboxyl groups, compared to using a compound having 4 or more carboxyl groups, the increase in viscosity of the semiconductor adhesive during storage, connection work, etc., can be further suppressed, thereby further improving the connection reliability of the semiconductor device.

[0089] (d) It is more preferable that the component be a compound having two carboxyl groups (dicarboxylic acid). In the case of a dicarboxylic acid, compared to a compound having one carboxyl group (monocarboxylic acid), it is less likely to volatilize even at high temperatures during connection, so the occurrence of voids can be further suppressed. In addition, using a compound having two carboxyl groups can further suppress the increase in viscosity of the semiconductor adhesive during storage and connection work compared to using a compound having three or more carboxyl groups, thereby further improving the connection reliability of the semiconductor device.

[0090] The melting point of component (d) is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher; preferably 250°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower. When the melting point of component (d) is 250°C or lower, flux activity is likely to be sufficiently expressed before the curing reaction between the thermosetting resin and the curing agent occurs. Therefore, according to the semiconductor adhesive containing such component (d), component (d) melts upon chip mounting and the oxide film on the solder surface is removed, thereby enabling the realization of a semiconductor device with even better connection reliability. Furthermore, when the melting point of component (d) is 50°C or higher, the reaction is difficult to initiate at room temperature or on a high-temperature stage, resulting in even better storage stability. From these perspectives, the melting point of component (d) is preferably 50 to 250°C, more preferably 60 to 150°C, and even more preferably 70 to 130°C.

[0091] (d) The melting point of the component can be measured using a general melting point measuring device. The sample for measuring the melting point is required to be ground into a fine powder and used in small quantities to minimize temperature variations within the sample. A capillary tube with one end closed is often used as the sample container, but depending on the measuring device, a container may be placed between two microscope cover glasses. Also, since a temperature gradient occurs between the sample and the thermometer when the temperature is raised rapidly, causing measurement errors, it is desirable to measure the heating at the time of measuring the melting point at a rate of increase of 1°C or less per minute.

[0092] As the sample for measuring the melting point is prepared as a fine powder as described above, the sample is opaque before melting due to diffuse reflection from the surface. It is common practice to set the temperature at which the sample begins to become transparent as the lower limit of the melting point and the temperature at which melting is completed as the upper limit. Although various types of measuring devices exist, the most classic device uses a double-tube thermometer with a capillary tube filled with the sample attached, which is heated in a hot bath. To attach the capillary tube to the double-tube thermometer, a highly viscous liquid is used as the bath liquid, often concentrated sulfuric acid or silicone oil, and the sample is mounted so that it is positioned near the saturation point at the tip of the thermometer. Additionally, as a melting point measuring device, a metal heat block may be used to heat the sample, and the melting point may be automatically determined by adjusting the heating while measuring the light transmittance.

[0093] Also, in this specification, "melting point 250°C or lower" means that the upper limit of the melting point is 250°C or lower, and "melting point 50°C or higher" means that the lower limit of the melting point is 50°C or higher.

[0094] Specific components of (d) include, for example, oxalic acid, malonic acid, α-ketoglutaric acid (2-oxoglutaric acid), 2,2'-thiodiglycolic acid, glycolic acid, 2-oxo-1,3-propanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, 3-phosphonopropionic acid, 4-phosphonobutyric acid, etc. Among these, oxalic acid, malonic acid, α-ketoglutaric acid, 2,2'-thiodiglycolic acid, and glycolic acid are preferred from the perspective of easily obtaining excellent flux activity and easily obtaining the effects of the present invention, and α-ketoglutaric acid is particularly preferred. These may be used individually or in combination of two or more types.

[0095] The content of component (d) is preferably 0.1 mass% or more based on the total solid content of the semiconductor adhesive. Also, the content of component (d) is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 2 mass% or less based on the total solid content of the semiconductor adhesive. From the perspective of connection reliability and downflow properties during semiconductor device fabrication, the content of component (d) is preferably 0.1 to 10 mass% based on the total solid content of the semiconductor adhesive, more preferably 0.1 to 5 mass%, and even more preferably 0.1 to 2 mass%. Additionally, if an organic acid corresponds to components (a) to (c), the content of component (d) is calculated by considering that the compound also corresponds to component (d).

[0096] In the present embodiment, the equivalent ratio (molar ratio of acidic functional groups / basic functional groups) of (d) the total amount of acidic functional groups to (c) the total amount of basic functional groups is preferably 1.0 or higher and preferably 3.0 or lower. More preferably, the equivalent ratio is 1.3 or higher, more preferably 1.5 or higher, more preferably 2.5 or lower, and even more preferably 2.0 or lower.

[0097] (e) Filler

[0098] The semiconductor adhesive of the present embodiment may, if necessary, contain a filler (component (e)). By component (e), the viscosity of the semiconductor adhesive and the physical properties of the cured product of the semiconductor adhesive can be controlled. Specifically, by component (e), for example, the suppression of void generation during connection and the reduction of the moisture absorption rate of the cured product of the semiconductor adhesive can be achieved.

[0099] (e) As a component, insulating inorganic fillers, whiskers, resin fillers, etc. may be used. Also, as a component of (e), one type may be used alone, or two or more types may be used in combination.

[0100] Examples of insulating inorganic fillers include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Among these, silica, alumina, titanium oxide, and boron nitride are preferred, and silica, alumina, and boron nitride are more preferred.

[0101] Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.

[0102] Examples of resin fillers include fillers made of resins such as polyuretaine and polyimide.

[0103] Resin fillers have a lower coefficient of thermal expansion compared to organic components (such as epoxy resins and curing agents), resulting in excellent improvement in connection reliability. Additionally, resin fillers allow for easy adjustment of the viscosity of semiconductor adhesives. Furthermore, resin fillers offer superior stress relief capabilities compared to inorganic fillers.

[0104] Since inorganic fillers have a lower coefficient of thermal expansion compared to resin fillers, they enable the realization of a low thermal expansion rate in adhesive compositions. Furthermore, because many inorganic fillers are general-purpose products with controlled particle sizes, they are also desirable for viscosity adjustment.

[0105] Since resin fillers and inorganic fillers each have advantageous effects, either one may be used depending on the application, or both may be mixed and used to exhibit the functions of both.

[0106] (e) The shape, particle size, and content of the component are not particularly limited. Additionally, the (e) component may have its physical properties appropriately adjusted by surface treatment.

[0107] (e) The content of the component is preferably 10 mass% or more, more preferably 15 mass% or more, preferably 80 mass% or less, and more preferably 60 mass% or less, based on the total solid content of the semiconductor adhesive. (e) The content of the component is preferably 10 to 80 mass%, and more preferably 15 to 60 mass%, based on the total solid content of the semiconductor adhesive.

[0108] (e) It is preferable that the component be composed of an insulating material. If the component (e) is composed of an insulating material, it is easier to suppress the degradation of insulation reliability (especially HAST resistance) compared to when it is composed of a conductive material (e.g., solder, gold, silver, copper, etc.).

[0109] (Other ingredients)

[0110] In the semiconductor adhesive of the present embodiment, additives such as antioxidants, silane coupling agents, titanium coupling agents, leveling agents, and ion trapping agents may be incorporated. These may be used individually or in combination of two or more types. The amounts of these additives may be appropriately adjusted so that the effects of each additive are expressed.

[0111] The semiconductor adhesive of the present embodiment may be in the form of a film. In this case, workability can be improved when sealing gaps between a semiconductor chip and a wiring substrate or gaps between multiple semiconductor chips using a pre-applied method. An example of a method for manufacturing the semiconductor adhesive of the present embodiment (film-type adhesive) formed into a film is shown below.

[0112] First, component (a), component (b), component (c), and component (d), and component (e) which is added as needed, are added in an organic solvent and dissolved or dispersed by stirring, mixing, kneading, etc. to prepare a resin varnish. Then, the resin varnish is applied to a substrate film that has undergone release treatment using a knife coater, a roll coater, an applicator, etc., and then the organic solvent is removed by heating to form a film-like adhesive on the substrate film.

[0113] The thickness of the film adhesive is not particularly limited, but, for example, it is preferably 0.5 to 1.5 times the height of the bump before connection, more preferably 0.6 to 1.3 times, and even more preferably 0.7 to 1.2 times.

[0114] If the thickness of the film-like adhesive is 0.5 times or more the height of the bump, the occurrence of voids due to insufficient adhesive filling can be sufficiently suppressed, thereby further improving connection reliability. Also, if the thickness is 1.5 times or less, the amount of adhesive extruded from the chip connection area during connection can be sufficiently suppressed, thus sufficiently preventing the adhesion of adhesive to unnecessary parts. If the thickness of the film-like adhesive is greater than 1.5 times, a large amount of adhesive must be excluded from the bump, making it prone to conduction failure. Furthermore, regarding the weakening of the bump (miniaturization of the bump diameter) due to narrow pitch and multi-pin, excluding a large amount of resin is undesirable because it causes significant damage to the bump.

[0115] Generally, if the height of the bump is 5 to 100 μm, the thickness of the film adhesive is preferably 2.5 to 150 μm, and more preferably 3.5 to 120 μm.

[0116] As for the organic solvent used in the preparation of the resin varnish, it is desirable that it has the characteristic of being able to uniformly dissolve or disperse each component, and examples include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. These organic solvents may be used alone or in combination of two or more types. Stirring, mixing, and kneading during the preparation of the resin varnish may be performed using, for example, a stirrer, a 3-roll mill, a ball mill, a bead mill, or a homodisperser.

[0117] As for the base film, there are no particular restrictions as long as it has heat resistance capable of withstanding the heating conditions when volatilizing an organic solvent, and examples include polyolefin films such as polypropylene films and polymethylpentene films, polyester films such as polyethylene terephthalate films and polyethylene naphthalate films, polyimide films, and polyetherimide films. The base film is not limited to a single layer made of these films, but may also be a multilayer film made of two or more materials.

[0118] When volatilizing the organic solvent from the resin varnish applied to the substrate film, the drying conditions should preferably be such that the organic solvent volatilizes sufficiently, and specifically, it is preferable to perform heating at 50 to 200°C for 0.1 to 90 minutes. It is preferable that the organic solvent be removed to 1.5 mass% or less relative to the total amount of the adhesive on the film.

[0119] In addition, the semiconductor adhesive of the present embodiment may be formed directly on the wafer. Specifically, for example, a layer made of the semiconductor adhesive may be formed directly on the wafer by spin-coating the resin varnish directly onto the wafer to form a film, and then removing the organic solvent.

[0120] The minimum melt viscosity of the semiconductor adhesive of the present embodiment is preferably 200 to 10,000 Pa·s, and more preferably 200 to 5,000 Pa·s, from the view that voids are more easily removed during curing under a pressurized atmosphere, thereby obtaining even better downflow properties. The minimum melt viscosity can be measured by the method described in the example. The temperature at which the semiconductor adhesive exhibits minimum melt viscosity (melting temperature) is preferably 100 to 250°C, more preferably 120 to 230°C, and even more preferably 140 to 200°C.

[0121] In the semiconductor adhesive of the present embodiment, from the view that the temporary fixation of a semiconductor chip in a temperature range of 60 to 170°C is easy, it is preferable that the melt viscosity at 80°C is 2,000 to 30,000 Pa·s, and it is preferable that the melt viscosity at 130°C is 400 to 20,000 Pa·s, and more preferably that the melt viscosity at 80°C is 4,000 to 20,000 Pa·s and the melt viscosity at 130°C is 400 to 5,000 Pa·s. The melt viscosity can be measured by the method described in the example.

[0122] The semiconductor adhesive of the present embodiment described above can be suitably used in a process of curing by applying heat under an atmospheric pressure or pressurized atmosphere. In particular, it can be suitably used in a process in which a plurality of semiconductor chips are mounted on a mounting member (semiconductor chip, semiconductor wafer, wiring circuit board, etc.) and temporarily fixed using the semiconductor adhesive, and then cured and sealed collectively under atmospheric pressure or pressurized conditions. When the semiconductor adhesive of the present embodiment is used in this process, voids within the adhesive are easily removed by atmospheric pressure or pressurization, making it easier to obtain even better downflow properties.

[0123] Semiconductor Device

[0124] The semiconductor device of the present embodiment is a semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other. In this semiconductor device, at least a portion of the connection portion is sealed by a cured product of the semiconductor adhesive that is cured by applying heat under atmospheric pressure or a heating atmosphere. Hereinafter, the semiconductor device of the present embodiment will be described with reference to FIGS. 1, 2, and 3. FIGS. 1, 2, and 3 are each cross-sectional views showing an embodiment of a semiconductor device that can be manufactured by a method according to the embodiment described below.

[0125] FIG. 1 is a schematic cross-sectional view showing a COB-type connection mode of a semiconductor chip and a substrate. The semiconductor device (100) shown in FIG. 1 comprises a semiconductor chip (1), a substrate (2) (wiring circuit board), and an adhesive layer (40) interposed between them. In the case of the semiconductor device (100), the semiconductor chip (1) has a semiconductor chip body (10), wiring or bumps (15) disposed on the surface of the semiconductor chip body (10) facing the substrate (2), and solder (30) as a connection part disposed on the wiring or bumps (15). The substrate (2) has a substrate body (20) and wiring or bumps (16) as a connection part disposed on the surface of the substrate body (20) facing the semiconductor chip (1). The solder (30) of the semiconductor chip (1) and the wiring or bumps (16) of the substrate (2) are electrically connected by a metal bond. The semiconductor chip (1) and the substrate (2) are flip-chip connected by wiring or bumps (16) and solder (30). The wiring or bumps (15, 16) and the solder (30) are sealed by an adhesive layer (40) so as to be isolated from the external environment.

[0126] FIG. 2 shows a COC type connection mode between semiconductor chips. The configuration of the semiconductor device (300) shown in FIG. 2 is identical to that of the semiconductor device (100), except that two semiconductor chips (1) are flip-chip connected via wiring or bumps (15) and solder (30).

[0127] In FIGS. 1 and 2, the connection portion, such as the wiring or bump (15), may be a metal film called a pad (e.g., gold plating) or a post electrode (e.g., copper filler).

[0128] As for the semiconductor chip body (10), there are no particular limitations, and various semiconductors such as elemental semiconductors composed of the same type of element, such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphorus can be used.

[0129] As for the substrate (2), there are no particular limitations on the wiring circuit board, and a circuit board in which wiring (wiring pattern) is formed by etching away unnecessary parts of a metal layer formed on the surface of an insulating substrate having glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine as the main component, a circuit board in which wiring (wiring pattern) is formed by metal plating, etc. on the surface of the insulating substrate, or a circuit board in which wiring (wiring pattern) is formed by printing a conductive material on the surface of the insulating substrate can be used.

[0130] As for the material of the connecting part, such as wiring or bumps (15 and 16) and solder (30), gold, silver, copper, solder (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel, etc., may be used as the main component, and may be composed of a single component or may be composed of multiple components. The connecting part may have a structure in which these metals are stacked. Among the metal materials, copper and solder are relatively inexpensive and are preferred. From the perspective of improving connection reliability and suppressing warping, the connecting part may include solder.

[0131] As for the material of the bump, gold, silver, copper, solder (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel, etc., may be used as the main component, and may be composed of a single component or may be composed of multiple components. The pad may have a structure in which these metals are laminated. From the perspective of connection reliability, the pad may contain gold or solder.

[0132] On the surface of the wiring or bump (15, 16) (wiring pattern), a metal layer may be formed with gold, silver, copper, solder (the main components being, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. This metal layer may be composed of only a single component or may be composed of multiple components. The metal layer may have a structure in which multiple metal layers are stacked. The metal layer may include copper or solder, which are relatively inexpensive. From the perspective of improving connection reliability and suppressing warping, the metal layer may include solder.

[0133] Semiconductor devices (packages) as shown in FIG. 1 or FIG. 2 may be stacked and electrically connected using gold, silver, copper, solder (the main components being, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel, etc. The metal for connection may be copper or solder, which are relatively inexpensive. For example, as seen in TSV technology, an adhesive layer may be interposed between semiconductor chips to perform flip-chip connection or stacking, and a hole penetrating the semiconductor chip may be formed to connect with an electrode on the pattern surface.

[0134] FIG. 3 is a cross-sectional view showing another embodiment of a semiconductor device (a semiconductor chip stacking type embodiment (TSV)). In the semiconductor device (500) shown in FIG. 3, the semiconductor chip (1) and the interposer (5) are flip-chip connected by connecting the wiring or bump (15) formed on the interposer body (50) as a substrate to the solder (30) of the semiconductor chip (1). An adhesive layer (40) is interposed between the semiconductor chip (1) and the interposer (5). On the surface opposite to the interposer (5) in the semiconductor chip (1), the semiconductor chip (1) is repeatedly stacked with the wiring and bump (15), solder (30), and adhesive layer (40) interposed. The wiring or bumps (15) on the pattern surface on the front and back of the semiconductor chip (1) are connected to each other by through electrodes (34) filled in a hole penetrating the inside of the semiconductor chip body (10). Copper, aluminum, etc., can be used as the material for the through electrodes (34).

[0135] With this TSV technology, signals can be obtained even from the back side of a semiconductor chip that is not normally used. Furthermore, since a through electrode (34) is passed vertically through the semiconductor chip (1), the distance between opposing semiconductor chips (1) and between the semiconductor chip (1) and the interposer (5) is shortened, allowing for flexible connection. The adhesive layer can be applied as a sealing material between opposing semiconductor chips (1) and between the semiconductor chip (1) and the interposer (5) in this TSV technology.

[0136] Method for manufacturing a semiconductor device

[0137] One embodiment of a method for manufacturing a semiconductor device comprises a stacking process in which a first member having a connection portion and a second member having a connection portion are stacked with a semiconductor adhesive interposed therebetween such that the connection portion of the first member and the connection portion of the second member are arranged facing each other, and a sealing process in which the semiconductor adhesive is cured by applying heat under atmospheric pressure or a pressurized atmosphere, and at least a portion of the connection portion is sealed by the cured semiconductor adhesive. Here, the first member is, for example, a wiring circuit board, a semiconductor chip, or a semiconductor wafer, and the second member is a semiconductor chip. In the sealing process, the stacked body obtained in the stacking process is heated under atmospheric pressure or a pressurized atmosphere to a temperature greater than or equal to the melting point of the connection portion arranged facing each other, thereby joining the connection portions arranged facing each other so that they are electrically connected.

[0138] When the first component is a semiconductor chip, the stacking process includes, for example, a process of placing a plurality of semiconductor chips on a stage, and a fixing process of sequentially placing another semiconductor chip on each of the plurality of semiconductor chips placed on the stage while heating the stage, with a semiconductor adhesive interposed thereon, and obtaining a plurality of stacked bodies (fixed bodies) formed by stacking the semiconductor chips, semiconductor adhesive, and other semiconductor chips in this order.

[0139] When the first component is a plurality of semiconductor chips on a wiring circuit board or a semiconductor wafer, the stacking process includes, for example, a process of placing a wiring circuit board or a semiconductor wafer on a stage, and a process of heating the stage while sequentially placing a plurality of semiconductor chips on the wiring circuit board or semiconductor wafer placed on the stage with a semiconductor adhesive interposed therebetween, and obtaining a stack (temporary fixed body) formed by stacking the wiring circuit board, the semiconductor adhesive, and the plurality of semiconductor chips in this order, or a stack (temporary fixed body) formed by stacking the semiconductor wafer, the semiconductor adhesive, and the plurality of semiconductor chips in this order.

[0140] In the temporary fixing process, for example, first, a semiconductor adhesive is placed on a first member or a second member (for example, attachment of a semiconductor adhesive on a film). Then, a semiconductor chip that has been fragmented on a dicing tape is picked up, adsorbed to a compression tool (compression head) of a compression machine, and temporarily fixed to a wiring circuit board, another semiconductor chip, or a semiconductor wafer.

[0141] The method of placing the semiconductor adhesive is not particularly limited; for example, if the semiconductor adhesive is in the form of a film, methods such as a heat press, roll lamination, or vacuum lamination may be used. The area and thickness of the semiconductor adhesive to be placed are appropriately determined by the size of the first and second members, the height of the connection portion (bump), etc. The semiconductor adhesive may be placed on the semiconductor chip, or the semiconductor wafer on which the semiconductor adhesive is placed may be diced and then reassembled into a semiconductor chip.

[0142] In the temporary fixing process, alignment is required to electrically connect the connection parts. For this reason, crimping machines such as flip-chip bonders are generally used.

[0143] When the compression tool picks up the semiconductor chip for temporary fixing, it is desirable for the compression tool to be at a low temperature so that heat is not transferred to the semiconductor adhesive on the semiconductor chip. Meanwhile, during compression (temperature compression), it is desirable for the semiconductor chip to be heated to a high temperature to increase the fluidity of the semiconductor adhesive and efficiently remove introduced voids. However, heating to a temperature lower than the initiation temperature of the curing reaction of the semiconductor adhesive is desirable. To shorten the cooling time, it is desirable for the difference between the temperature of the compression tool when picking up the semiconductor chip and the temperature of the compression tool during temporary fixing to be small. This temperature difference is preferably 100°C or less, more preferably 60°C or less, and substantially 0°C more desirable. If the temperature difference is 100°C or more, it takes time to cool the compression tool, so productivity tends to decrease. The onset temperature of the curing reaction of a semiconductor adhesive refers to the onset temperature measured using a DSC (PerkinElmer Inc., DSC-Pyirs1) under conditions of a sample amount of 10 mg, a heating rate of 10°C / min, and an air or nitrogen atmosphere.

[0144] The load applied for temporary fixation is appropriately set by considering the number of connection parts (bumps), absorption of height non-uniformity of the connection parts (bumps), and the amount of deformation of the connection parts (bumps). In the temporary fixation process, it is desirable for opposing connection parts to be in contact with each other after compression (temporary compression). If the connection parts are in contact with each other after compression, metal bonding of the connection parts is easily formed during compression (main compression) in the sealing process, and there is a tendency for the semiconductor adhesive to curl in less. To eliminate voids and ensure contact of the connection parts, the load should be larger; for example, 0.0001N to 0.2N per connection part (e.g., bump) is preferable, 0.009N to 0.2N is more preferable, and 0.001N to 0.1N is even more preferable.

[0145] The compression time of the temporary fixing process is preferably shorter from the perspective of improving productivity, and for example, it may be 5 seconds or less, 3 seconds or less, or 2 seconds or less.

[0146] The heating temperature of the stage is a temperature lower than the melting point of the connection portion of the first member and the melting point of the connection portion of the second member, and may typically be 60 to 155°C, 65 to 120°C, or 70 to 100°C. By heating at such a temperature, voids introduced into the semiconductor adhesive can be efficiently removed. In addition, the heating temperature of the stage is not actually applied to the adhesive itself.

[0147] As described above, it is preferable to set the temperature of the crimping tool during temporary fixing so that the temperature difference from the temperature of the crimping tool when picking up the semiconductor chip is small, but for example, it may be 80 to 350°C or 100 to 170°C.

[0148] When the stacking process includes the above-mentioned temporary fixing process, in the sealing process following the temporary fixing process, the semiconductor adhesive in the stack having a plurality of stacks or a plurality of semiconductor chips may be cured collectively or in separate portions, and the plurality of connection parts may be sealed collectively or in separate portions. Through the sealing process, opposing connection parts are joined by a metal bond, and typically, the gap between the connection parts is filled with the semiconductor adhesive. The sealing process is performed using a device capable of heating above the melting point of the metal of the connection part and capable of applying pressure. Examples of such devices include a pressurized reflow furnace and a pressurized oven.

[0149] The heating temperature (connection temperature) of the sealing process is preferably heated at a temperature above the melting point of at least one of the metals among the opposing connection parts (e.g., bump-bump, bump-pad, bump-wiring). For example, if the metal of the connection part is solder, a temperature of 200°C or higher and 450°C or lower is preferable. If the heating temperature is low, the metal of the connection part may not melt, and there is a possibility that a sufficient metal bond may not be formed. If the heating temperature is excessively high, the effect of void suppression tends to be relatively reduced, or the solder tends to scatter easily.

[0150] If pressure is applied for bonding the connection portion using a press, heat from the press is difficult to transfer to the semiconductor adhesive (fillet) protruding from the side of the connection portion. Consequently, it is often necessary to perform additional heat treatment after the press (main press) to sufficiently cure the semiconductor adhesive. For this reason, it is preferable to apply pressure during the sealing process using air pressure within a pressurized oven or pressurized reflow, rather than a press. Pressurization by air pressure allows heat to be applied to the entire process, thereby shortening or eliminating the heat treatment after the press (main press), which improves productivity. Furthermore, pressurization by air pressure facilitates the simultaneous main press of multiple laminates (temporary fixed bodies) or laminates (temporary fixed bodies) comprising multiple temporarily fixed semiconductor chips. Additionally, pressurization by air pressure is preferable to direct pressurization using a press, from the perspective of fillet suppression. Fillet suppression is important in light of the trend toward miniaturization and high-density semiconductor devices.

[0151] The atmosphere in which compression is performed during the sealing process is not particularly limited, but an atmosphere containing air, nitrogen, formic acid, etc. is preferred.

[0152] The compression pressure in the sealing process is appropriately set according to the size and number of connected members, etc. The pressure may, for example, exceed atmospheric pressure and be 1 MPa or less. A higher pressure is preferable from the perspective of void suppression and improved connectivity, while a lower pressure is preferable from the perspective of fillet suppression. Therefore, a pressure of 0.05 to 0.5 MPa is more preferable.

[0153] The crimping time varies depending on the constituent metal of the connection part, but a shorter time is preferable from the perspective of improving productivity. When the connection part is a solder bump, the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and more preferably 5 seconds or less. In the case of copper-copper or copper-gold metal connections, the connection time is preferably 60 seconds or less.

[0154] In the case where multiple semiconductor chips are stacked three-dimensionally, such as in a semiconductor device with a TSV structure, the semiconductor device may be obtained by stacking multiple semiconductor chips one by one to a fixed state, and then heating and pressurizing the stacked multiple semiconductor chips collectively.

[0155] Examples

[0156] The present disclosure will be explained more specifically below by way of examples, but the present disclosure is not limited to examples.

[0157] The compounds used in each example and comparative example are as follows.

[0158] (a) Component: Thermoplastic resin

[0159] · Phenoxy resin (manufactured by Shin-Nippon Tetsuya Sumitomo Metal Corporation, product name "FX293", Tg: approx. 160℃, Mw: approx. 40000)

[0160] · Polyurethane (manufactured by DIC Covestro Polymer Co., Ltd., trade name "T-8175N", Tg: -23℃, Mw: 120000)

[0161] (b) Component: Thermosetting resin

[0162] · Polyfunctional solid epoxy containing triphenolmethane backbone (Manufactured by Mitsubishi Chemical Corporation, Trade name "EP1032H60")

[0163] · Bisphenol F-type liquid epoxy (manufactured by Mitsubishi Chemical Corporation, product name "YL983U")

[0164] · Liquid Epoxy X (Manufactured by Mitsubishi Chemical Corporation, product name "YX")

[0165] (c) Ingredient: Curing agent

[0166] · 2,4-Diamino-6-[2'-methylimidazoleyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei High School Co., Ltd., trade name "2MAOK-PW", Mw: 384)

[0167] (d) Components: Organic acid

[0168] · Glutaric acid (Manufactured by Fujifilm Wako Junyaku Co., Ltd., Melting point: 98℃, Mw: 132)

[0169] · Diglycolic acid (Manufactured by Tokyo Kasei High School Co., Ltd., Melting point: 144℃, Mw: 134)

[0170] ·2,2'-Thiodiglycolic acid (Manufactured by Tokyo Kasei High School Co., Ltd., Melting point: 131℃, Mw: 150)

[0171] ·α-ketoglutarate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., Melting point: 118℃, Mw: 146)

[0172] · Benzilic acid (Manufactured by Fujifilm Wako Junyaku Co., Ltd., Melting point: 152℃, Mw: 228)

[0173] (e) Filler

[0174] · Methacrylic surface-treated silica filler (Manufactured by Admatex Co., Ltd., trade name "180nm SM-EH1", average particle size approx. 180nm)

[0175] · Silica filler (Manufactured by Admatex Co., Ltd., product name "SE2030", average particle size 0.5μm)

[0176] · Epoxysilane surface-treated silica filler (Manufactured by Admatex Co., Ltd., product name "SE2030-SEJ", average particle size 0.5μm)

[0177] · Methacrylic surface-treated silica filler (Manufactured by Admatex Co., Ltd., trade name "YA050C-SM1", average particle size approx. 0.05μm)

[0178] (a) The weight-average molecular weight (Mw) of the component was determined by the GPC method. The details of the GPC method are as follows.

[0179] Device Name: HPLC-8020 (Product Name, Manufactured by Dosho Co., Ltd.)

[0180] Column: 2pieces of GMHXL+1piece of G-2000XL

[0181] Detector: RI detector

[0182] Column temperature: 35℃

[0183] Flow rate: 1 mL / min

[0184] Standard material: Polystyrene

[0185] <Fabrication of Film-based Semiconductor Adhesives>

[0186] The thermoplastic resin, thermosetting resin, curing agent, organic acid, and filler in the amounts (unit: parts by mass) shown in Table 1 were added to an organic solvent (cyclohexanone) such that the NV value ([mass of paint after drying] / [mass of paint before drying] × 100) was 50%. Then, 1.0 mm zirconia beads and 2.0 mm zirconia beads of the same mass as the amount of solids (thermoplastic resin, thermosetting resin, curing agent, organic acid, and filler) were added to the same container and stirred for 30 minutes using a ball mill (Fritz Japan Co., Ltd., planetary fine grinder P-7). After stirring, the zirconia beads were removed by filtration, and a coating varnish was produced.

[0187] The obtained coated varnish was coated onto a substrate film (manufactured by Teijin DuPont Film Co., Ltd., product name "Purex A55") using a small precision coating device (manufactured by Yasui Seiki Co., Ltd.) and dried (100℃ / 10 min) in a clean oven (manufactured by ESPEC) to obtain a film-like adhesive with a film thickness of 20 μm.

[0188] The following describes the evaluation method for the film-like adhesives obtained in the examples and comparative examples. The evaluation results are shown in Tables 1 and 2.

[0189] <DSC 측정>

[0190] 10 mg of the obtained film-like adhesive was weighed into an aluminum pan (manufactured by Epolly Service Co., Ltd.), covered with an aluminum lid, and the evaluation sample was sealed inside the sample pan using a crimper. Using a differential scanning calorimeter (Thermo plus DSC8235E, manufactured by Rigaku Co., Ltd.), measurements were taken under a nitrogen atmosphere at a heating rate of 10°C / min and a measurement temperature range of 30 to 300°C. As a means of analyzing the onset temperature, the analysis method of the entire area (JIS method) was used, and by instructing the analysis in the temperature range of 60 to 250°C, the intersection point of the baseline of the peak and the maximum slope point in each DSC curve was calculated to obtain the onset temperature (unit: °C). Meanwhile, as a means of analyzing the heat of ignition, the same analysis method of the entire area (JIS method) was used, and by instructing the analysis in the temperature range of 60 to 250°C, the heat of ignition (unit: J / g) was calculated by performing the integration of the peaks in each DSC curve.

[0191] High-temperature stability evaluation

[0192] The film-like adhesive (initial sample) obtained in the example and comparative example was placed in an oven set to 50°C and heat-treated for 3 hours, then placed in an oven set to 70°C and heat-treated for 3 hours, and the sample was removed to obtain evaluation sample A after heat treatment.

[0193] Evaluation sample A was used, and a differential scanning calorimeter (Thermo plus DSC8235E, manufactured by Rigaku Co., Ltd.) was used in the same order as before heat treatment to calculate the heat of 60 to 250°C (unit: J / g). This was taken as the heat of the heat after heat treatment.

[0194] Using the two obtained heat values ​​(heat of the initial sample and heat of evaluation sample A), the reaction rate was calculated using the following formula.

[0195] Reaction rate (%) = (Initial heat generation - Heat generation after heat treatment) / Initial heat generation × 100

[0196] Void Evaluation

[0197] (Fabrication of laminate C (temporary body C) after compression)

[0198] The film adhesive (initial sample) obtained in the above examples and comparative examples was made to a film thickness of 40 μm using a desktop laminator (product name: Hotdog GK-13DX, manufactured by Lamy Corporation), cut into a 7.5 mm square size, and attached to a plurality of solder bump-attached semiconductor chips (chip size: 7.3 mm × 7.3 mm, thickness 0.1 mm, bump (connection part) height: approximately 45 μm (total of copper filler and solder), number of bumps: 1048 pins, pitch 80 μm, product name: WALTS-TEG CC80, manufactured by Walts Co., Ltd.) at 80°C. A semiconductor chip with a film adhesive attached was sequentially compressed and temporarily fixed by heating and pressing with a flip chip bonder (FCB3, Panasonic Corporation) onto another semiconductor chip (chip size: 10 mm × 10 mm, thickness 0.1 mm, number of bumps: 1048 pins, pitch 80 μm, product name: WALTS-TEG IP80, manufactured by Walts Co., Ltd.) to obtain a laminate C (temporarily fixed) after compression. The compression conditions were set to 130°C, 75 N, and 3 seconds.

[0199] The laminate (temporary fixed body C) after the above compression was placed in an oven set to 80°C and heat treated for 6 hours, after which a sample was removed to obtain the laminate D (temporary fixed body D) after compression and heat treatment at 80°C.

[0200] The laminate D (pre-fixed body D) after the above compression was placed inside the oven of a pressure oven device (manufactured by NTT Advance Technology Co., Ltd.). The pressure inside the oven was set to 0.8 MPa, and the temperature was raised from room temperature to 190°C at a heating rate of 20°C / min. Subsequently, while maintaining the pressure and temperature, the compressed body was heated under a pressurized atmosphere for 1 hour to obtain an evaluation mounting sample E.

[0201] (Interpretation / Evaluation)

[0202] An external image of the above-mentioned evaluation mounting sample was captured using an ultrasound imaging diagnostic device (product name: Insight-300, manufactured by Insight Co., Ltd.).

[0203] [Measurement Conditions]

[0204] Probe frequency: 180 MHz

[0205] Diagnostic Mode: Echo (Pulse Reflection Method)

[0206] From the obtained image, the image of the adhesive layer between the chips was read using a scanner (GT-9300UF, manufactured by Seiko Epson Corporation). In the read image, void areas were identified using image processing software (Adobe Photoshop (product name)) through color correction and second-order harmonics, and the proportion occupied by the void area was calculated using a histogram. The total area of ​​the adhesive layer including the void area was defined as 100%. A case where the void area ratio was less than 10% was designated as "A", a case where the void area ratio was 10% or more but less than 30% was designated as "B", and a case where it was 30% or more was designated as "C". The evaluation results are shown in Table 1.

[0207] <Check for cracks in the connection part>

[0208] (Fabrication of laminate F (temporary body F) after compression)

[0209] The film adhesive (initial sample) obtained in the above examples and comparative examples was made to a film thickness of 40 μm using a desktop laminator (product name: Hotdog GK-13DX, manufactured by Lamy Corporation), cut into a 7.5 mm square size, and attached to a plurality of solder bump-attached semiconductor chips (chip size: 7.3 mm × 7.3 mm, thickness 0.1 mm, bump (connection part) height: approximately 45 μm (total of copper filler and solder), number of bumps: 1048 pins, pitch 80 μm, product name: WALTS-TEG CC80, manufactured by Walts Co., Ltd.) at 80°C. A semiconductor chip with a film adhesive attached was sequentially compressed and temporarily fixed by heating and pressing with a flip chip bonder (FCB3, Panasonic Corporation) against another semiconductor chip (chip size: 10 mm × 10 mm, thickness: 0.1 mm, number of bumps: 1048 pins, pitch: 80 μm, product name: WALTS-TEG IP80, manufactured by Walts Co., Ltd.) to obtain a laminate F (temporarily fixed F) after compression. The compression conditions were as follows: compression was performed while applying heat in stages at 190°C / 25 N / 10 seconds, 260°C / 25 N / 20 seconds, and 100°C / 25 N / 5 seconds (set heating time for each heating step: 0.1 seconds).

[0210] The laminate F (pre-fixed body F) after the above compression was placed inside the oven of a pressure oven device (manufactured by NTT Advance Technology Co., Ltd.). The pressure inside the oven was set to 0.8 MPa, and the temperature was raised from room temperature to 190°C at a heating rate of 20°C / min. Subsequently, while maintaining the pressure and temperature, the compressed body was heated under a pressurized atmosphere for 1 hour to obtain an evaluation mounting sample G.

[0211] For the above-mentioned evaluation sample, a bench polisher (Refine Polisher, manufactured by Refinetec Co., Ltd.) was used to polish the bump connection portion inside the chip until it was exposed. As for the water-resistant abrasive paper used for polishing, a size of 200 cmφ and a grit of 1000 were initially used, and then replaced with a water-resistant abrasive paper of 2000 grit, and polished until the connection portion was exposed. Afterward, further polishing was performed using alumina liquid (suspension liquid) A-0.3 micron (manufactured by Refinetec Co., Ltd.). The exposed bump connection portion was observed using an SEM (TM3030Plus bench microscope, manufactured by Hitachi High Technology Co., Ltd.) to check for the presence of cracks inside the solder and at the solder-Cu wiring interface.

[0212] <Evaluation of Connectivity>

[0213] For the obtained evaluation mounting sample G, connectivity was evaluated by measuring the resistance value inside the chip using a circuit tester (POCKET TESTER 4300 COUNT, manufactured by CUSTOM). The circuit diagram of the lower chip used for mounting (chip size: 7.3mm × 7.3mm, thickness 0.1mm, bump (connection part) height: approximately 45μm (total of copper filler and solder), number of bumps: 1048 pins, pitch 80μm, product name: WALTS-TEG CC80, manufactured by Walts Co., Ltd.) is shown in Fig. 4. In this circuit, the resistance value between terminal a and terminal b in the figure becomes the resistance value inside the chip. If this resistance value is less than 35Ω, it indicates good connectivity, and if it is 35Ω or more, or if the resistance value cannot be measured, it indicates poor connectivity.

[0214] Evaluation of Solder Wetness

[0215] For the above-mentioned evaluation sample, the cross-section of the connection part was observed using SEM in the same way as the crack verification of the connection part, and the case where the solder wets more than 90% of the upper surface of the Cu wiring was evaluated as "A" (good), and the case where the solder wetness is less than 90% was evaluated as "B" (insufficient wetness).

[0216] [Table 1]

[0217]

[0218] [Table 2]

[0219] Explanation of the symbols

[0220] 1… semiconductor chip 2… board 10… semiconductor chip body 15, 16… Wiring or bump 20… circuit board body 30… solder 34… penetrating electrode 40… adhesive layer 50… Interposer main body 100, 300, 500… semiconductor device

Claims

Claim 1 A semiconductor adhesive comprising a thermoplastic resin, a thermosetting resin, a curing agent, and an organic acid, wherein the organic acid is a compound having two or more acidic functional groups and an acid dissociation constant pKa of 4.0 or less, and the equivalent ratio of the acidic functional group included in the organic acid to the basic functional group included in the curing agent is 1.0 or more and 3.0 or less. Claim 2 A semiconductor adhesive according to claim 1, wherein the acidic functional group comprises at least one group selected from the group consisting of a carboxyl group, a sulfoxyl group, and a phosphate group. Claim 3 delete Claim 4 A semiconductor adhesive according to claim 1, wherein the organic acid comprises a compound represented by the following general formula (1-1), (1-2), or (1-3). [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Equations (1-1), (1-2) and (1-3), R 1 represents an electronic absorbing device, and R 2 represents a hydrogen atom or an electron-withdrawing group, and R 3 represents a hydrogen atom or a monovalent organic group, X represents an oxygen atom or a sulfur atom, and n 1 represents an integer from 0 to 15, and n 2 and n 3 are respectively, n 2 +n 3 This represents an integer greater than or equal to 1 selected to be an integer between 2 and 15, where m represents 1 or 2. Additionally, there are multiple R 3 They may be identical or different. Claim 5 A semiconductor adhesive according to claim 1, wherein the melting point of the organic acid is 50 to 250°C. Claim 6 A semiconductor adhesive according to claim 1, wherein the curing agent comprises an amine-based curing agent. Claim 7 A semiconductor adhesive according to claim 1, wherein the curing agent comprises an imidazole-based curing agent. Claim 8 A semiconductor adhesive according to claim 7, wherein the structure of the imidazole-based curing agent comprises a triazine ring. Claim 9 A semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, comprising a method for manufacturing a semiconductor device comprising a sealing process in which a semiconductor adhesive described in any one of claims 1, 2, and 4 to 8 is cured by applying heat under atmospheric pressure or a pressurized atmosphere, and at least a portion of the connection portion is sealed by the cured semiconductor adhesive. Claim 10 A method for manufacturing a semiconductor device according to claim 9, further comprising, prior to the sealing process, a process of placing a plurality of semiconductor chips on a stage, and a process of heating the stage to 60 to 155°C, sequentially placing another semiconductor chip on each of the plurality of semiconductor chips placed on the stage with the semiconductor adhesive interposed therebetween, and obtaining a plurality of laminates formed by stacking the semiconductor chip, the semiconductor adhesive, and the other semiconductor chip in this order. Claim 11 A method for manufacturing a semiconductor device according to claim 9, further comprising, prior to the sealing process, a process of placing a wiring circuit board or a semiconductor wafer on a stage, and a process of heating the stage to 60 to 155°C while sequentially placing a plurality of semiconductor chips on the wiring circuit board or semiconductor wafer placed on the stage with the semiconductor adhesive interposed therebetween, and obtaining a laminate formed by stacking the wiring circuit board, the semiconductor adhesive, and the plurality of semiconductor chips in this order, or a laminate formed by stacking the semiconductor wafer, the semiconductor adhesive, and the plurality of semiconductor chips in this order. Claim 12 A semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, wherein at least a portion of the connection portion is sealed by a cured product of a semiconductor adhesive described in any one of claims 1, 2, and 4 to 8, which is cured by applying heat under atmospheric pressure or a pressurized atmosphere.

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