Adhesive for semiconductor, method for manufacturing semiconductor device, and semiconductor device

Abstract

A semiconductor adhesive comprising (a) an inorganic filler, wherein the (a) inorganic filler contains 50% by mass or more of an inorganic filler surface-treated to have a glycidyl group, based on the total amount of the (a) inorganic filler.

Description

Technical Field

[0001] The present invention relates to a semiconductor adhesive, a method for manufacturing a semiconductor device, and a semiconductor device. Background Art

[0002] In the past, when connecting a semiconductor chip to a substrate, a wire bonding method using a thin metal wire such as a gold wire was widely used. On the other hand, in order to meet the requirements for high functionality, high integration, and high speed of semiconductor devices, a flip chip connection method (FC connection method) is being promoted, which forms a conductive protrusion called a bump on a semiconductor chip or substrate to directly connect the semiconductor chip to the substrate.

[0003] As FC connection methods, there are known methods of metal bonding the connection parts using solder, tin, gold, silver, copper, etc., methods of metal bonding the connection parts by applying ultrasonic vibration, methods of maintaining mechanical contact by the shrinkage force of resin, etc. However, from the viewpoint of the reliability of the connection parts, the method of metal bonding the connection parts using solder, tin, gold, silver, copper, etc. is generally used.

[0004] For example, regarding the connection between a semiconductor chip and a substrate, the COB (Chip On Board) type connection method popularly used in BGA (Ball grid Array) and CSP (Chip Size Package) is also equivalent to the FC connection method. In addition, the FC connection method is also widely used in the COC (Chip On Chip) type connection method in which a connection portion (bump or wiring) is formed on a semiconductor chip to connect semiconductor chips, and the COW (Chip On Wafer) type connection method in which a connection portion (bump or wiring) is formed on a semiconductor wafer to connect a semiconductor chip and a semiconductor wafer (for example, refer to Patent Document 1).

[0005] Furthermore, in the case of packages that are strongly demanded to be further miniaturized, thinned, and highly functional, chip stacking packages, POP (Package On Package), TSV (Through-Silicon Via), etc., which are formed by stacking and multi-layering the above-mentioned connection methods, have also begun to become widely popular. Since this stacking and multi-layering technology configures semiconductor chips and the like in three dimensions, it is possible to reduce the package size compared to the method of two-dimensional configuration. Furthermore, since this stacking and multi-layering technology is also effective in improving semiconductor performance, reducing noise, reducing mounting area, and saving power, it has attracted much attention as the next generation of semiconductor wiring technology.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2016-102165 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] As for the flip chip package, which has advanced in functionality, integration, and cost, it is expected that its use will be further expanded and the production volume will be increased accordingly. When the flip chip package is continuously mass-produced, the semiconductor adhesive used must be continuously supplied, so the semiconductor adhesive is required to have excellent stability over time. If the semiconductor adhesive has poor stability over time, the viscosity of the semiconductor adhesive will increase when it is placed at room temperature, and the installation performance during the assembly of the semiconductor device may be deteriorated.

[0011] Therefore, an object of the present invention is to provide a semiconductor adhesive that can suppress viscosity increase after standing at room temperature and is less likely to deteriorate in mounting properties during semiconductor device assembly over time, as well as a method for manufacturing a semiconductor device using the semiconductor adhesive and a semiconductor device.

[0012] Means for solving technical problems

[0013] To achieve the above-mentioned object, the present invention provides a semiconductor adhesive, which contains (a) an inorganic filler, and the (a) inorganic filler contains 50% or more of the inorganic filler surface-treated with glycidyl groups, based on the total amount of the (a) inorganic filler. According to the semiconductor adhesive, by setting more than 50% by mass of the (a) inorganic filler as the inorganic filler surface-treated with glycidyl groups, the viscosity increase caused by the influence of moisture absorption during standing at room temperature can be suppressed. For example, in the case of inorganic fillers that have been subjected to other surface treatments such as surface treatments with methacrylic groups, the surface treatment agent forms hydrogen bonds with moisture and the viscosity increase is likely to occur, but in the case of inorganic fillers that have been subjected to surface treatments with glycidyl groups, it is not easy to form hydrogen bonds with moisture, so that the viscosity increase is not easy to occur. In addition, according to the semiconductor adhesive, since the viscosity increase after standing at room temperature can be suppressed, the deterioration of the mounting property during the assembly of the semiconductor device over time can be suppressed. Furthermore, by subjecting the inorganic filler to a surface treatment having a glycidyl group, the inorganic filler has excellent dispersibility in the semiconductor adhesive, and the semiconductor adhesive can obtain good bonding strength and good insulation reliability.

[0014] The adhesive for semiconductors may further contain (b) an epoxy resin, (c) a curing agent, and (d) a high molecular weight component having a weight average molecular weight of 10000 or more. Furthermore, the adhesive for semiconductors may further contain (e) a flux.

[0015] The semiconductor adhesive may be in a film form, in which case the semiconductor adhesive can be easily handled, thereby improving the workability and productivity during package manufacturing.

[0016] Furthermore, the present invention provides a method for manufacturing a semiconductor device, wherein the semiconductor device is a semiconductor device in which the connection portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which the connection portions of a plurality of semiconductor chips are electrically connected to each other, and the method for manufacturing a semiconductor device includes: a step of sealing at least a portion of the connection portion using the semiconductor adhesive. According to the manufacturing method, the semiconductor adhesive used is less likely to increase in viscosity over time, and thus good mounting properties can be stably obtained.

[0017] Furthermore, the present invention provides a semiconductor device, which comprises: a connection structure in which the connection parts of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a connection structure in which the connection parts of a plurality of semiconductor chips are electrically connected to each other, and an adhesive material for sealing at least a part of the connection part, wherein the adhesive material is formed of a cured product of the semiconductor adhesive. The semiconductor device has good mountability, and the bonding strength and reliability between the semiconductor chip and the wiring circuit board or the semiconductor chip are excellent.

[0018] Effects of the Invention

[0019] According to the present invention, a semiconductor adhesive that can suppress viscosity increase after standing at room temperature and is less likely to deteriorate in mounting properties during semiconductor device assembly over time, as well as a method for manufacturing a semiconductor device using the semiconductor adhesive and a semiconductor device can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic cross-sectional view showing one embodiment of a semiconductor device according to the present invention.

[0021] Figure 2 It is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

[0022] Figure 3 It is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

[0023] Figure 4 It is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. DETAILED DESCRIPTION

[0024] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, as appropriate. In addition, in the accompanying drawings, the same or equivalent parts are marked with the same symbols, and repeated descriptions are omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right refer to those based on the positional relationships shown in the accompanying drawings. In addition, the dimensional ratios of the accompanying drawings are not limited to the ratios shown in the drawings.

[0025] In this specification, the numerical range represented by "~" indicates a range that includes the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. In the numerical range recorded in stages in this specification, the upper limit value or the lower limit value of the numerical range of a certain stage can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of other stages. In the numerical range recorded in this specification, the upper limit value or the lower limit value of the numerical range can also be replaced by the value shown in the embodiment. The so-called "A or B" only needs to include any one of A and B, and can also include both at the same time. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. In this specification, the so-called "(meth) acrylic acid" refers to acrylic acid or its corresponding methacrylic acid.

[0026] <Adhesives for semiconductors>

[0027] The semiconductor adhesive involved in this embodiment contains (a) an inorganic filler (hereinafter, referred to as "(a) component" as the case may be). Based on the total amount of (a) inorganic filler, the above-mentioned (a) inorganic filler contains 50% by mass or more of an inorganic filler that has been surface-treated to have a glycidyl group. In addition, the semiconductor adhesive involved in this embodiment may contain one or more of (b) an epoxy resin (hereinafter, referred to as "(b) component" as the case may be), (c) a curing agent (hereinafter, referred to as "(c) component" as the case may be), and (d) a high molecular weight component with a weight average molecular weight of more than 10,000 (hereinafter, referred to as "(d) component" as the case may be). Furthermore, the semiconductor adhesive involved in this embodiment may contain (e) a flux (hereinafter, referred to as "(e) component" as the case may be). Each component is described below.

[0028] ((a) Ingredient: Inorganic filler)

[0029] Inorganic fillers as component (a) include insulating inorganic fillers and the like. Among them, inorganic fillers with an average particle size of less than 100 nm are more preferred. Materials of the insulating inorganic filler include glass, silica, alumina, silica·alumina, titanium oxide, mica, boron nitride, etc., among which silica, alumina, silica·alumina, titanium oxide, and boron nitride are preferred, and silica, alumina, and boron nitride are more preferred. The insulating inorganic filler may also be a whisker, and materials of the whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, boron nitride, etc. The insulating inorganic filler may be used alone or in combination of two or more.

[0030] From the viewpoint of improving dispersibility and adhesive strength, component (a) is preferably a surface-treated filler. Examples of the surface treatment include glycidyl-based (epoxy-based), amine-based, phenyl-based, phenylamino-based, acrylic-based, and vinyl-based fillers.

[0031] As a surface treatment, silane treatment using silane compounds such as epoxysilane, aminosilane, and acrylic silane is preferred in terms of ease of surface treatment. As a surface treatment agent, glycidyl, phenylamino, and (meth)acrylic acid compounds are preferred in terms of excellent dispersibility and fluidity and further improved adhesive strength. As a surface treatment agent, glycidyl compounds are preferred in terms of suppressing the increase in viscosity of the semiconductor adhesive after being left at room temperature.

[0032] In the present embodiment, based on the total amount of component (a), component (a) contains 50% by mass or more of an inorganic filler that has been surface-treated with a glycidyl group. The surface treatment with a glycidyl group can be performed using a glycidyl-based compound having a structure represented by the following general formula (1) as a surface treatment agent. Thus, the inorganic filler has a structure represented by the following general formula (1) on the surface.

[0033] [Chemical formula 1]

[0034]

[0035] In the formula, R represents a divalent organic group.

[0036] The content of the inorganic filler having a surface treatment having a glycidyl group is 50% by mass or more based on the total amount of component (a), preferably 60% by mass or more, and more preferably 80% by mass or more from the viewpoint of further suppressing the increase in viscosity of the adhesive for semiconductor after being left at room temperature. The total amount (100% by mass) of component (a) may also be the inorganic filler having a surface treatment having a glycidyl group.

[0037] From the viewpoint of improving visibility (transparency), the average particle size of the component (a) is preferably 100 nm or less, and more preferably 60 nm or less. The average particle size of the component (a) can be measured by a laser diffraction particle size distribution analyzer.

[0038] Furthermore, if the average particle size of the component (a) exceeds 100 nm, the viscosity of the semiconductor adhesive may become too low due to the large particle size, and the resin may easily overflow to the outside of the chip called fillet after the semiconductor chip is mounted. In contrast, if the average particle size of the component (a) is 100 nm or less, the viscosity of the semiconductor adhesive may be easily adjusted to a preferred range, and the generation of fillet may be sufficiently suppressed, or the amount of fillet may be sufficiently reduced.

[0039] The lower limit of the average particle size of the component (a) is not particularly limited, but from the viewpoint of suppressing the aggregation of the component (a), it may be 1 nm or more, 5 nm or more, or 10 nm or more. When an inorganic filler that has not been surface treated is used, aggregation may occur even if the average particle size is about 50 nm, but when an inorganic filler that has been surface treated with a glycidyl group is used, the generation of aggregation can be suppressed even if the average particle size is about 50 nm or less.

[0040] The component (a) can be used alone or as a mixture of two or more thereof. The shape of the component (a) is not particularly limited.

[0041] Based on the total solid content of the semiconductor adhesive, the content of component (a) is preferably 10% to 80% by mass, more preferably 15% to 60% by mass, and further preferably 20% to 50% by mass. If the content is 10% by mass or more, there is a tendency to further improve the bonding strength and reflow resistance, and if it is 80% by mass or less, there is a tendency to suppress the decrease in connection reliability due to viscosity increase.

[0042] The semiconductor adhesive according to the present embodiment may contain a resin filler. As the resin filler, for example, fillers containing resins such as polyurethane and polyimide can be cited. Compared with other organic components (epoxy resin and curing agent, etc.), the resin filler has a small thermal expansion coefficient, so it is excellent in improving the connection reliability. In addition, the viscosity of the semiconductor adhesive can be easily adjusted according to the resin filler. In addition, compared with inorganic fillers, the resin filler has an excellent function of relieving stress.

[0043] From the viewpoint of insulation reliability, the filler contained in the semiconductor adhesive is preferably insulating. The semiconductor adhesive preferably does not contain conductive metal fillers such as silver fillers and solder fillers. The semiconductor adhesive (circuit connection material) that does not contain conductive fillers (conductive particles) is sometimes also referred to as NCF (Non-Conductive-FILM) or NCP (Non-Conductive-Paste). The semiconductor adhesive involved in this embodiment can be preferably used as NCF or NCP.

[0044] ((b) ingredient: epoxy resin)

[0045] The epoxy resin of component (b) includes epoxy resins having two or more epoxy groups in the molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, various multifunctional epoxy resins, etc. Component (b) can be used alone or in combination of two or more.

[0046] Among epoxy resins, bisphenol A type or bisphenol F type liquid epoxy resins have a 1% thermal weight loss temperature of 250°C or less, so they may decompose and generate volatile components when heated at high temperatures. Therefore, it is preferred to use an epoxy resin that is solid at room temperature (1 atmosphere, 25°C). When using a liquid epoxy resin, it is preferably used in combination with a solid epoxy resin.

[0047] The weight average molecular weight of the component (b) may be less than 10,000, but is preferably 100 or more and less than 10,000, more preferably 300 or more and 8,000 or less, and even more preferably 300 or more and 5,000 or less from the viewpoint of heat resistance.

[0048] Based on the total solid content of the adhesive for semiconductors, the content of component (b) is preferably 10% to 50% by mass, more preferably 20% to 45% by mass, and further preferably 30% to 40% by mass. If the content of component (b) is 10% by mass or more, it is easy to fully control the flow of the cured resin, and if it is 50% by mass or less, the resin component of the cured product will not become excessive, and it is easy to reduce the warping of the package.

[0049] The adhesive for semiconductors according to the present embodiment may further contain other thermosetting resins other than the above-mentioned (b) epoxy resin. Examples of other thermosetting resins include phenol resins, imide resins, and (meth)acrylic compounds.

[0050] ((c) component: curing agent)

[0051] As the (c) curing agent, there can be listed: phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents and phosphine curing agents. If the (c) component contains phenolic hydroxyl groups, acid anhydrides, amines or imidazoles, it is easy to show the flux activity that suppresses the generation of oxide films in the connection parts, thereby easily improving the connection reliability and insulation reliability. The following is a description of each curing agent.

[0052] (ci) Phenolic resin curing agent

[0053] As the phenol resin curing agent, there can be cited curing agents having two or more phenolic hydroxyl groups in the molecule, and can be used: phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type multifunctional phenol resin, various multifunctional phenol resins, etc. The phenol resin curing agent can be used alone or in combination of two or more.

[0054] From the viewpoint of excellent curability, adhesion and storage stability, the equivalent ratio (phenolic hydroxyl group / epoxy group, molar ratio) of the phenol resin curing agent to the above-mentioned component (b) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and further preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, there is a tendency for improved curability and improved adhesive strength, and if it is 1.5 or less, there is no excess residual unreacted phenolic hydroxyl group, the water absorption rate is suppressed to be low, and there is a tendency for further improved insulation reliability.

[0055] (c-ii) Anhydride curing agent

[0056] As the acid anhydride curing agent, methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis-trimellitic anhydride ester, etc. The acid anhydride curing agent can be used alone or in combination of two or more.

[0057] From the viewpoint of excellent curability, adhesion and storage stability, the equivalent ratio (anhydride group / epoxy group, molar ratio) of the acid anhydride curing agent to the above-mentioned component (b) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and further preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, there is a tendency for improved curability and improved adhesive strength, and if it is 1.5 or less, there is no excess residual unreacted acid anhydride, the water absorption rate is suppressed to be low, and there is a tendency for further improved insulation reliability.

[0058] (c-iii) Amine curing agent

[0059] As the amine-based curing agent, dicyandiamide, various amine compounds, and the like can be used.

[0060] From the viewpoint of excellent curability, adhesion and storage stability, the equivalent ratio (amine / epoxy group, molar ratio) of the amine curing agent to the above-mentioned component (b) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and further preferably 0.5 to 1.0. If the equivalent ratio is 0.3 or more, there is a tendency for improved curability and improved adhesive strength, and if it is 1.5 or less, there is no excess residual unreacted amine, and there is a tendency for further improved insulation reliability.

[0061] (c-iv) Imidazole curing agent

[0062] Examples of the imidazole curing agent include 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'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, adducts of epoxy resins and imidazoles, etc. Among these, 1-cyanoethyl-2-undecyl imidazole, 1-cyano-2-phenyl imidazole, 1-cyanoethyl-2-undecyl imidazole trimellitate, 1-cyanoethyl-2-phenyl imidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl imidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred from the viewpoint of being more excellent in curing property, storage stability and connection reliability. The imidazole curing agent can be used alone or in combination of two or more. Furthermore, these may be microencapsulated to form a latent curing agent.

[0063] The content of the imidazole curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of component (b). If the content of the imidazole curing agent is 0.1 parts by mass or more, there is a tendency for the curability to be improved, and if it is 20 parts by mass or less, the adhesive composition will not cure before the metal bonding is formed, and there is a tendency that poor connection is not easy to occur.

[0064] (cv) Phosphine-based curing agent

[0065] Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis(4-methylphenyl)borate, and tetraphenylphosphonium(4-fluorophenyl)borate.

[0066] The content of the phosphine curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the component (b). If the content of the phosphine curing agent is 0.1 parts by mass or more, the curability tends to be improved, and if it is 10 parts by mass or less, the semiconductor adhesive will not cure before the metal bonding is formed, and there is a tendency that poor connection is not easy to occur.

[0067] Phenolic resin curing agents, acid anhydride curing agents and amine curing agents can be used alone or in combination of two or more. Imidazole curing agents and phosphine curing agents can be used alone or together with phenolic resin curing agents, acid anhydride curing agents or amine curing agents.

[0068] As (c) component, from the viewpoint of excellent curability, preferably use phenol resin type curing agent and imidazole type curing agent and anhydride type curing agent and imidazole type curing agent and amine type curing agent and imidazole type curing agent, use imidazole type curing agent alone.If connected in a short time, productivity improves, therefore more preferably use the imidazole type curing agent of excellent fast curability alone.In this case, if solidified in a short time, then can suppress the volatile components such as low molecular weight components, therefore also can easily suppress the generation of space.

[0069] (Component (d): high molecular weight component having a weight average molecular weight of 10,000 or more)

[0070] As (d) high molecular weight components having a weight average molecular weight of 10,000 or more (excluding compounds corresponding to component (b)), there can be listed: phenoxy resins, polyimide resins, polyamide resins, polycarbodiimide resins, cyanate resins, (meth) acrylic resins, polyester resins, polyethylene resins, polyether sulfone resins, polyether imide resins, polyvinyl acetal resins, polyurethane resins, acrylic rubbers, etc. Among them, from the viewpoint of excellent heat resistance and film-forming properties, phenoxy resins, polyimide resins, (meth) acrylic resins, acrylic rubbers, cyanate resins, polycarbodiimide resins are preferred, phenoxy resins, polyimide resins, (meth) acrylic resins, acrylic rubbers are more preferred, and phenoxy resins are further preferred. Component (d) can also be used alone or as a mixture or copolymer of two or more.

[0071] The mass ratio of component (d) to component (b) is not particularly limited. From the perspective of maintaining a good film shape, the content of component (b) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and further preferably 0.1 to 3 parts by mass relative to 1 part by mass of component (d). If the content of component (b) is 0.01 parts by mass or more, the curability will not be reduced or the adhesive strength will not be reduced. If the content is 5 parts by mass or less, the film-forming property and film-forming property will not be reduced.

[0072] The weight average molecular weight of component (d) is 10,000 or more in terms of polystyrene conversion, and is preferably 30,000 or more, more preferably 40,000 or more, and further preferably 50,000 or more in order to show good film-forming properties alone. When the weight average molecular weight is 10,000 or more, the film-forming properties will not be reduced. In addition, in this specification, the so-called weight average molecular weight refers to the weight average molecular weight when measured by polystyrene conversion using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).

[0073] ((e) ingredient: flux)

[0074] The semiconductor adhesive may further contain a compound that exhibits flux activity (activity to remove oxides, impurities, etc.), namely (e) a flux. Examples of flux include nitrogen-containing compounds having unshared electron pairs (imidazoles, amines, etc., excluding compounds included in component (c)), carboxylic acids, phenols, and alcohols. In addition, carboxylic acids exhibit flux activity more strongly than alcohols, and are likely to improve connectivity.

[0075] From the viewpoint of solder wettability, the content of the component (e) is preferably 0.2% by mass to 3% by mass, and more preferably 0.4% by mass to 1.8% by mass, based on the total solid content of the binder for a semiconductor.

[0076] The semiconductor adhesive may further contain: an ion trapping agent, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, etc. These may be used alone or in combination of two or more. The amount of these may be appropriately adjusted in such a way that the effects of each additive are exhibited.

[0077] The shear viscosity at 80°C when the semiconductor adhesive is made into a film is preferably 4500Pa·s to 14000Pa·s, more preferably 5000Pa·s to 13000Pa·s, and further preferably 5000Pa·s to 10000Pa·s. By having a shear viscosity of 4500Pa·s or more, the generation of fillet can be sufficiently suppressed or the amount of fillet can be sufficiently reduced. By having a shear viscosity of 14000Pa·s or less, the mountability during assembly of the semiconductor device can be improved. The shear viscosity of the semiconductor adhesive made into a film can be measured, for example, using a dynamic shear viscoelasticity measuring device (manufactured by TAInstruments Japan Inc., trade name "ARES-G2", etc.) under the conditions of a heating rate of 10°C / min, a measuring temperature range of 30°C to 145°C, and a frequency of 10Hz. The viscosity value measured by the above method at 80°C can be obtained as the shear viscosity at 80°C of the semiconductor adhesive when it is made into a film.

[0078] <Method for producing semiconductor adhesive>

[0079] From the viewpoint of improving productivity, the adhesive for semiconductors according to the present embodiment is preferably in the form of a film (film-like adhesive). A method for producing the film-like adhesive will be described below.

[0080] First, after adding component (a), component (b), component (c), component (d) and other components as needed to an organic solvent, the resin varnish is dissolved or dispersed by stirring, mixing, kneading, etc. Then, the resin varnish is applied to the substrate film subjected to the demolding treatment using a scraper, a roll coater, an applicator, a die coater, a comma coater, etc., and the organic solvent is reduced by heating to form a film-like adhesive on the substrate film. In addition, the film-like adhesive can also be formed on the wafer by the following method, that is, before the organic solvent is reduced by heating, the resin varnish is spin-coated on the wafer to form a film, and then the solvent is dried.

[0081] The organic solvent used in the preparation of the resin varnish preferably has the property of being able to dissolve or disperse each component uniformly, and examples thereof include: dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. These organic solvents can be used alone or in combination of two or more. The stirring, mixing, and kneading when preparing the resin varnish can be carried out using, for example, a stirrer, a crusher, a three-roller, a ball mill, a beads mill, or a homogenizer.

[0082] The substrate film is not particularly limited as long as it has heat resistance that can withstand the heating conditions for volatilizing the organic solvent, and examples thereof include polyester films, polypropylene films, polyethylene terephthalate films, polyimide films, polyetherimide films, polyether naphthalate films, methylpentene films, etc. The substrate film is not limited to a single-layer film composed of one of these films, and may be a multilayer film composed of two or more films.

[0083] Specifically, the conditions for volatilizing the organic solvent from the applied resin varnish are preferably heating at 50°C to 200°C for 0.1 to 90 minutes. As long as the gap after mounting and viscosity adjustment are not affected, the organic solvent is preferably volatilized to 1.5% by mass or less.

[0084] The thickness of the film in the film-like adhesive according to the present embodiment is preferably 10 μm to 100 μm, more preferably 20 μm to 50 μm, from the viewpoints of visibility, fluidity, and filling properties.

[0085] <Semiconductor devices>

[0086] The semiconductor adhesive involved in this embodiment can be preferably used in a semiconductor device, and can be particularly preferably used for sealing the connection portion in a semiconductor device in which the electrodes of the connection portions of a semiconductor chip and a wiring circuit substrate are electrically connected to each other, or in a semiconductor device in which the electrodes of the connection portions of a plurality of semiconductor chips are electrically connected to each other. The semiconductor device using the semiconductor adhesive involved in this embodiment is described below. The electrodes of the connection portion in the semiconductor device can be either a metal connection between a bump and a wiring, or a metal connection between bumps. In the semiconductor device, for example, a flip chip connection that obtains an electrical connection via a semiconductor adhesive can be used.

[0087] Figure 1 Schematic cross-sectional view showing an embodiment of a semiconductor device (a COB type connection method of a semiconductor chip and a substrate). Figure 1As shown in (a), the first semiconductor device 100 has a semiconductor chip 10 and a substrate (wiring circuit substrate) 20 facing each other, wiring 15 respectively arranged on the facing surfaces of the semiconductor chip 10 and the substrate 20, a connection bump 30 connecting the wiring 15 of the semiconductor chip 10 and the substrate 20 to each other, and an adhesive material 40 seamlessly filling the gap between the semiconductor chip 10 and the substrate 20. The semiconductor chip 10 and the substrate 20 are connected by flip chip through the wiring 15 and the connection bump 30. The wiring 15 and the connection bump 30 are sealed by the adhesive material 40 and isolated from the external environment. The adhesive material 40 is a cured product of the semiconductor adhesive of this embodiment.

[0088] like Figure 1 As shown in (b), the second semiconductor device 200 has a semiconductor chip 10 and a substrate (wiring circuit substrate) 20 facing each other, bumps 32 respectively arranged on the facing surfaces of the semiconductor chip 10 and the substrate 20, and an adhesive material 40 seamlessly filled in the gap between the semiconductor chip 10 and the substrate 20. The semiconductor chip 10 and the substrate 20 are connected to each other through the facing bumps 32 and are connected by flip chip. The bumps 32 are sealed by the adhesive material 40 and isolated from the external environment.

[0089] Figure 2 FIG. 1 is a schematic cross-sectional view showing another embodiment of a semiconductor device (a COC type connection method between semiconductor chips). Figure 2 As shown in (a) of FIG. 1 , the third semiconductor device 300 is the same as the first semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wiring 15 and connection bumps 30. Figure 2 As shown in (b) of FIG. 1 , the fourth semiconductor device 400 is the same as the second semiconductor device 200 except that two semiconductor chips 10 are flip-chip connected by bumps 32 .

[0090] The semiconductor chip 10 is not particularly limited, and various semiconductors can be used, such as element semiconductors made of the same element such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphide.

[0091] The substrate 20 is not particularly limited as long as it is a wiring circuit substrate, and can be used: a circuit substrate having wiring (wiring pattern) formed by etching away unnecessary parts of a metal layer formed on the surface of an insulating substrate having glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin, etc. as the main components; a circuit substrate having wiring (wiring pattern) formed on the surface of the above-mentioned insulating substrate by metal plating, etc.; a circuit substrate having wiring (wiring pattern) formed on the surface of the above-mentioned insulating substrate by printing a conductive material on the surface of the above-mentioned insulating substrate, etc.

[0092] The connection parts such as the wiring 15 and the bump 32 contain gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper), nickel, tin, lead, etc. as main components, and may contain multiple metals.

[0093] On the surface of the wiring (wiring pattern), a metal layer with gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. as the main component may also be formed. The metal layer may be composed of only a single component or a plurality of components. In addition, it may be formed into a structure in which a plurality of metal layers are stacked. Copper and solder are widely used because they are cheap. In addition, copper and solder contain oxides, impurities, etc., so the semiconductor adhesive preferably has fluxing activity.

[0094] As the material of the conductive protrusion called a bump, gold, silver, copper, solder (the main component is, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. can be used as the main component, which can be composed of only a single component or a plurality of components. Moreover, it can also be formed in a way that a structure formed by stacking these metals is formed. The bump can also be formed on a semiconductor chip or a substrate. Copper and solder are commonly used because they are cheap. In addition, copper and solder contain oxides, impurities, etc., so the semiconductor adhesive preferably has fluxing activity.

[0095] Also, stackable Figure 1 or Figure 2 The semiconductor device (package) shown in the figure is electrically connected by gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. For example, as seen in TSV technology, an adhesive can be interposed between semiconductor chips to perform flip chip connection or stacking, forming a hole that penetrates the semiconductor chip and is connected to the electrode on the pattern surface.

[0096] Figure 3 Schematic cross-sectional view showing another embodiment of a semiconductor device (a semiconductor chip stacking method (TSV)). Figure 3As shown, in the fifth semiconductor device 500, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bump 30, thereby flip-chip connecting the semiconductor chip 10 and the interposer 50. The gap between the semiconductor chip 10 and the interposer 50 is filled with an adhesive material 40 without a gap. On the surface of the semiconductor chip 10 on the side opposite to the interposer 50, the semiconductor chip 10 is repeatedly stacked via the wiring 15, the connection bump 30 and the adhesive material 40. The wiring 15 on the pattern surface of the surface and the back of the semiconductor chip 10 is connected to each other through the through electrode 34 filled in the hole penetrating the inside of the semiconductor chip 10. In addition, as the material of the through electrode 34, copper, aluminum, etc. can be used.

[0097] Through this TSV technology, signals can be obtained from the back side of a semiconductor chip that is usually not used. Furthermore, since the through electrode 34 is vertically penetrated in the semiconductor chip 10, the distance between the opposing semiconductor chips 10 or between the semiconductor chip 10 and the interposer 50 can be shortened, and flexible connection can be performed. The semiconductor adhesive involved in this embodiment can be preferably used as a sealing material between the opposing semiconductor chips 10 or between the semiconductor chip 10 and the interposer 50 in this TSV technology.

[0098] <Method for manufacturing semiconductor device>

[0099] The method for manufacturing a semiconductor device according to the present embodiment is to connect a semiconductor chip and a wiring circuit board, or a plurality of semiconductor chips to each other using the semiconductor adhesive according to the present embodiment. The method for manufacturing a semiconductor device according to the present embodiment includes, for example, a step of connecting a semiconductor chip and a wiring circuit board to each other via a semiconductor adhesive, and electrically connecting the connection portions of the semiconductor chip and the wiring circuit board to each other to obtain a semiconductor device; or a step of connecting a plurality of semiconductor chips to each other via a semiconductor adhesive, and electrically connecting the connection portions of the plurality of semiconductor chips to each other to obtain a semiconductor device.

[0100] In the method for manufacturing a semiconductor device according to the present embodiment, the connection portions can be connected to each other by metal bonding, that is, the connection portions of a semiconductor chip and a wiring circuit board can be connected to each other by metal bonding, or the connection portions of a plurality of semiconductor chips can be connected to each other by metal bonding.

[0101] As an example of a method for manufacturing a semiconductor device according to this embodiment, Figure 41 and 2. The sixth semiconductor device 600 shown in FIG. 1 is described in detail. In the sixth semiconductor device 600, a substrate (e.g., a glass epoxy substrate) 60 having wiring (copper wiring) 15 and a semiconductor chip 10 having wiring (e.g., a copper pillar, a copper post) 15 are connected to each other via an adhesive material 40. The wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are electrically connected via a connection bump (solder bump) 30. On the surface of the substrate 60 where the wiring 15 is formed, a flux resist 70 is arranged outside the formation position of the connection bump 30.

[0102] In the manufacturing method of the sixth semiconductor device 600, first, a semiconductor adhesive (film adhesive, etc.) is attached to the substrate 60 formed with the flux resist 70. The attachment can be performed by heat stamping, roller lamination, vacuum lamination, etc. The supply area and thickness of the semiconductor adhesive can be appropriately set according to the size of the semiconductor chip 10 or the substrate 60, the bump height, etc. The semiconductor adhesive can be attached to the semiconductor chip 10, or the semiconductor adhesive can be attached to the semiconductor wafer and then sliced ​​(dicing) to form a semiconductor chip 10, thereby making a semiconductor chip 10 attached with the semiconductor adhesive. In this case, if the semiconductor adhesive has a high transmittance, visual recognition can be ensured even if the alignment mark is covered, so the attachment range is not limited not only on the semiconductor wafer (semiconductor chip) but also on the substrate, and the operability is excellent.

[0103] After the semiconductor adhesive is attached to the substrate 60 or the semiconductor chip 10, the connection bump 30 on the wiring 15 of the semiconductor chip 10 is aligned with the wiring 15 of the substrate 60 using a connection device such as a flip chip bonding machine. Then, the semiconductor chip 10 and the substrate 60 are heated and pressed at a temperature above the melting point of the connection bump 30 (when solder is used in the connection part, it is preferably applied to the solder part at 240°C or above), so that the semiconductor chip 10 and the substrate 60 are connected, and the semiconductor adhesive is cured, and the gap between the semiconductor chip 10 and the substrate 60 is sealed and filled by the adhesive material 40 composed of the cured product of the semiconductor adhesive. The connection load depends on the number of bumps, but it should be set in consideration of absorbing the uneven height of the bumps, controlling the deformation of the bumps, etc. From the perspective of improving productivity, the connection time is preferably short. It is preferred to melt the solder to remove the oxide film, surface impurities, etc., and form a metal joint at the connection part.

[0104] The short connection time (crimping time) means that the time during which the connection is heated to 240°C or higher (for example, when solder is used) is 10 seconds or less. The connection time is preferably 5 seconds or less, more preferably 3 seconds or less.

[0105] In the method for manufacturing a semiconductor device of the present embodiment, temporary fixing (via the state of a semiconductor adhesive) may also be performed after alignment, and a heat treatment may be performed in a reflow furnace, thereby melting the solder bump and connecting the semiconductor chip to the substrate, thereby manufacturing a semiconductor device. Temporary fixing does not significantly require the formation of a metal joint, so compared with the above-mentioned formal crimping, it can be low load, short time, and low temperature, resulting in advantages such as improved productivity and prevention of degradation of the connection portion. After the semiconductor chip is connected to the substrate, the semiconductor adhesive may also be further cured by heat treatment using an oven or the like. The heating temperature is a temperature at which the semiconductor adhesive is cured, preferably substantially completely cured. The heating temperature and heating time can be appropriately set.

[0106] The manufacturing method of the semiconductor device involved in this embodiment may be a method comprising the following steps in sequence: a step of temporarily crimping a substrate, other semiconductor chips or a semiconductor wafer to a semiconductor chip by clamping the stacked body with a pair of opposing temporary crimping pressing parts to heat and pressurize it (temporary crimping step), wherein the stacked body comprises a semiconductor chip; a substrate, other semiconductor chips or a semiconductor wafer including a portion equivalent to other semiconductor chips; and a semiconductor adhesive (film adhesive) arranged therebetween, and a connecting portion of the semiconductor chip and a connecting portion of the substrate or other semiconductor chips are arranged opposite to each other; and a step of electrically connecting the connecting portion of the semiconductor chip and a connecting portion of the substrate or other semiconductor chips by metal bonding (formal crimping step).

[0107] In the above-mentioned manufacturing method, when the stack is heated and pressurized, at least one of the pair of temporary pressing parts used in the temporary pressing process is heated to a temperature lower than the melting point of the metal material on the surface of the connection portion forming the semiconductor chip and the melting point of the metal material on the surface of the connection portion forming the substrate or other semiconductor chip.

[0108] On the other hand, in the formal compression bonding process, the laminate is heated to a temperature above the melting point of the metal material forming the surface of the connection portion of the semiconductor chip, or the melting point of the metal material forming the surface of the connection portion of the substrate or other semiconductor chips. Here, the formal compression bonding process can be performed, for example, by the following method.

[0109] (First method)

[0110] The stack is clamped by a pair of pressing members for formal crimping that are separately prepared and opposed to the pressing members for temporary crimping, and the connection portion of the semiconductor chip is electrically connected to the connection portion of the substrate or other semiconductor chips through metal bonding. In this case, when the stack is heated and pressurized, at least one of the pair of pressing members for formal crimping is heated to a temperature higher than the melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the melting point of the metal material forming the surface of the connection portion of the substrate or other semiconductor chips.

[0111] According to the above method, different pressing parts for crimping are used to perform a process of temporary crimping at a temperature lower than the melting point of the metal material on the surface forming the connection portion, and a process of formal crimping at a temperature above the melting point of the metal material on the surface forming the connection portion, thereby shortening the time required for heating and cooling each pressing part for crimping. Therefore, semiconductor devices can be manufactured in a shorter time and with good productivity than crimping using one pressing part for crimping. As a result, a large number of highly reliable semiconductor devices can be manufactured in a short time. Connections can be made uniformly in the formal crimping process. In the case of uniform connection, more semiconductor chips are crimped in the formal crimping compared to temporary crimping, so a pressing part for crimping with a large crimping head can be used. If multiple semiconductor chips can be uniformly crimped as described to ensure connection, the productivity of the semiconductor device is improved.

[0112] (Second method)

[0113] By clamping a plurality of stacked bodies arranged on the platform or a stacked body having a plurality of semiconductor chips, semiconductor wafers and adhesives and a unified connection sheet arranged to cover the stacked bodies by using a platform and a crimping head opposed to the platform, the plurality of stacked bodies are uniformly heated and pressurized, thereby electrically connecting the connection portion of the semiconductor chip to the connection portion of the substrate or other semiconductor chips through metal bonding. In this case, at least one of the platform and the crimping head is heated to a temperature higher than the melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the melting point of the metal material forming the surface of the connection portion of the substrate or other semiconductor chips.

[0114] According to the above method, when a plurality of semiconductor chips are subjected to final compression bonding at once with a plurality of substrates, a plurality of other semiconductor chips, or a semiconductor wafer, the proportion of semiconductor devices with poor connection can be reduced.

[0115] The raw materials of the unified connection sheet are not particularly limited, and examples thereof include polytetrafluoroethylene resin, polyimide resin, phenoxy resin, epoxy resin, polyamide resin, polycarbodiimide resin, cyanate resin, acrylic resin, polyester resin, polyethylene resin, polyether sulfone resin, polyetherimide resin, polyvinyl acetal resin, carbamate resin, and acrylic rubber. From the perspective of excellent heat resistance and film forming properties, the unified connection sheet may be a sheet comprising at least one resin selected from polytetrafluoroethylene resin, polyimide resin, epoxy resin, phenoxy resin, acrylic resin, acrylic rubber, cyanate resin, and polycarbodiimide resin. From the perspective of particularly excellent heat resistance and film forming properties, the resin of the unified connection sheet may be a sheet comprising at least one resin selected from polytetrafluoroethylene resin, polyimide resin, phenoxy resin, acrylic resin, and acrylic rubber. These resins can be used alone or in combination of two or more.

[0116] (Third Method)

[0117] The stack is heated in a heating furnace or on a hot plate to a temperature above the melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the melting point of the metal material forming the surface of the connection portion of the substrate or other semiconductor chips.

[0118] In the case of the above method, by performing the temporary crimping process and the formal crimping process separately, the time required for heating and cooling the pressing member for temporary crimping can be shortened. Therefore, it is possible to manufacture semiconductor devices with a shorter time and good productivity than crimping using a single crimping pressing member. As a result, a large number of highly reliable semiconductor devices can be manufactured in a short time. In addition, in the above method, a plurality of laminates can be uniformly heated in a heating furnace or on a heating plate. Thus, semiconductor devices can be manufactured with higher productivity.

[0119] In this manufacturing method in which the temporary crimping process and the formal crimping process are performed separately, after the temporary crimping of a plurality of stacked bodies, the temporary crimped plurality of stacked bodies can be uniformly subjected to formal crimping. However, at this time, it is required that the quality of the first and last temporarily crimped stacked bodies after formal crimping does not deviate. That is, the first temporarily crimped stacked body is kept in the temporary crimping state for a longer time than the last temporarily crimped stacked body. Therefore, it is required that the semiconductor adhesive used does not easily increase in viscosity from the beginning to the end of the temporary crimping process. The semiconductor adhesive (film adhesive) involved in this embodiment can suppress the increase in viscosity over time, and thus can meet the above requirements, and can be preferably used in the above manufacturing method.

[0120] Example

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0122] The compounds used in each of the Examples and Comparative Examples are as follows.

[0123] (a) Inorganic fillers

[0124] Epoxy surface treated nano silica filler (an inorganic filler subjected to surface treatment with a glycidyl group, manufactured by Admatechs Co., Ltd., trade name “50nm SE-AH1”, average particle size: about 50nm, hereinafter referred to as “SE nano silica”)

[0125] Methacrylic acid surface treated nanosilica filler (manufactured by Admatechs Co., Ltd., trade name "50nm YA050C-HGF", average particle size: about 50nm, hereinafter referred to as "YA nanosilica")

[0126] (b) Epoxy resin

[0127] ·Trisphenolmethane skeleton-containing multifunctional solid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "EP1032H60", hereinafter referred to as "EP1032")

[0128] · Flexible epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YL7175", hereinafter referred to as "YL7175")

[0129] (c) Curing agent

[0130] 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (manufactured by SHIKOKU CHEMICALS CORPORATION, trade name "2MAOK-PW", hereinafter referred to as "2MAOK")

[0131] (d) High molecular weight component having a weight average molecular weight of 10,000 or more

[0132] Acrylic resin (manufactured by Kuraray Co., Ltd., trade name "Kurarity LA4285", Mw / Mn=1.28, weight average molecular weight Mw: 80,000, hereinafter referred to as "LA4285")

[0133] (e) Flux

[0134] Glutaric acid (manufactured by Sigma-Aldrich Japan, melting point: about 97°C)

[0135] <Production of film adhesive>

[0136] (Example 1)

[0137] Epoxy resin "EP1032" 12.4g, "YL7175" 0.72g, curing agent "2MAOK" 0.9g, glutaric acid 1.2g, inorganic filler "SE nano silica" 33.9g, acrylic resin "LA4285" 6.0g, and cyclohexanone (making the solid content in the resin varnish 49% by mass) were added, and zirconia beads with a diameter of 1.0mm of the same mass as the solid content were added, and stirred for 30 minutes using a glass bead mill (Fritsch Japan Co., Ltd., manufactured, planetary micro-pulverizer P-7). Then, the zirconia beads used for stirring were removed by filtration to obtain a resin varnish.

[0138] The obtained resin varnish was applied to a substrate film (manufactured by Teijin Dupont Film Japan Limited, trade name "Purex A54") using a small precision coating device (manufactured by Yasui Seiki Inc.), and the applied resin varnish was dried (100°C / 5 minutes) in a clean oven (manufactured by ESPEC Corp.) to obtain a film-like adhesive. The film was prepared to have a thickness of 0.02 mm.

[0139] (Example 2)

[0140] A film-like adhesive was prepared in the same manner as in Example 1 except that the inorganic filler "SE nanosilica" was reduced to 17 g and 17 g of the inorganic filler "YA nanosilica" was added.

[0141] (Comparative Example 1)

[0142] A film-like adhesive was prepared in the same manner as in Example 1 except that the inorganic filler "SE nanosilica" was removed and 33.9 g of the inorganic filler "YA nanosilica" was added.

[0143] Table 1 summarizes the formulations of Examples 1 and 2 and Comparative Example 1 (unit: g).

[0144] <Evaluation>

[0145] The evaluation method of the film-like adhesives obtained in Examples and Comparative Examples is shown below.

[0146] (1) Preparation of samples for shear viscosity measurement

[0147] A plurality of the prepared film adhesives were laminated (stacked) using a tabletop laminator (manufactured by Lami Corporation, trade name "HOTDOG gK-13DX") until the total thickness became 0.4 mm (400 μm), and then cut into pieces having a length of 7.3 mm and a width of 7.3 mm to obtain measurement samples.

[0148] (2) Determination of shear viscosity

[0149] The shear viscosity of the obtained measurement sample was measured using a dynamic shear viscoelasticity measuring device (manufactured by TA Instruments Japan Inc., trade name "ARES-G2"). The measurement was carried out under the measurement conditions of a heating rate of 10°C / min, a measurement temperature range of 30°C to 145°C, and a frequency of 10 Hz, and the viscosity value at 80°C was read. By the same method, the shear viscosity of the measurement sample after being placed at room temperature (23°C, 50% RH) for 4 weeks was measured. The measurement results of the shear viscosity before and after being placed at room temperature, and the viscosity increase rate before and after being placed at room temperature are shown in Table 2.

[0150] [Table 1]

[0151]

[0152] [Table 2]

[0153]

[0154] According to the evaluation results in Table 2, it is confirmed that in the film adhesives of Example 1 and Example 2, in which the inorganic filler with a surface treatment having a glycidyl group accounts for more than 50% by mass of the total inorganic filler, the viscosity increase rate before and after standing at room temperature is less than 20%, and the viscosity increase over time is suppressed. Regarding the film adhesives of these Examples 1 and 2, since the viscosity increase over time is suppressed, it is not easy to deteriorate the mounting performance during the assembly of the semiconductor device over time. On the other hand, it is known that in the film adhesive of Comparative Example 1, in which the inorganic filler with a surface treatment having a glycidyl group accounts for less than 50% by mass of the total inorganic filler, the viscosity increase rate before and after standing at room temperature is more than 80%, and the viscosity is easy to increase over time.

[0155] Explanation of symbols

[0156] 10-semiconductor chip, 15-wiring, 20, 60-substrate, 30-connection bump, 32-bump, 34-through electrode, 40-adhesive material, 50-intermediate layer, 70-flux resist, 100, 200, 300, 400, 500, 600-semiconductor device.

Claims

1. A semiconductor adhesive comprising (a) an inorganic filler, (b) an epoxy resin, (c) a curing agent, and (d) a high molecular weight component having a weight average molecular weight of 10,000 or more, wherein the inorganic filler (a) comprises 50% by mass or more of an inorganic filler surface-treated to have a glycidyl group, based on the total amount of the inorganic filler (a), the content of the inorganic filler (a) is 33.9 / 55.12×100% by mass to 80% by mass, based on the total solid content of the semiconductor adhesive, and the inorganic filler (a) consists only of an inorganic filler having an average particle size of 100 nm or less. 2 . The adhesive for semiconductor according to claim 1 , further comprising (e) a flux. The adhesive for semiconductor according to claim 1 or 2, which is in a film form.

4. A method for manufacturing a semiconductor device, wherein the semiconductor device is a semiconductor device in which the connection parts of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which the connection parts of a plurality of semiconductor chips are electrically connected to each other, The method for manufacturing a semiconductor device comprises: A step of sealing at least a portion of the connection portion using the semiconductor adhesive according to any one of claims 1 to 3.

5. A semiconductor device comprising: A connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other; and an adhesive material that seals at least a portion of the connection, The adhesive material is formed of a cured product of the adhesive for semiconductor according to any one of claims 1 to 3.

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