Film-like adhesive for semiconductor, method for producing film-like adhesive for semiconductor, adhesive tape, method for producing semiconductor device, and semiconductor device

Abstract

This film-like adhesive for semiconductors has, along the thickness direction, a first adhesive region that does not contain a flux compound and a second adhesive region that contains a flux compound, the first adhesive region containing a first epoxy resin, a first imidazole-based curing agent, and a (meth) acrylic compound, and the second adhesive region containing a second imidazole-based curing agent. The second adhesive region includes a second epoxy resin, a second imidazole-based curing agent, and a flux compound.

Description

Technical Field

[0001] The present invention relates to a film adhesive for semiconductor, a method for producing the film adhesive for semiconductor, an adhesive tape, a method for producing a semiconductor device, and a semiconductor device. Background Art

[0002] In the past, when connecting semiconductor chips and substrates, wire bonding using fine metal wires such as gold wires was widely used. On the other hand, in order to meet the requirements for high functionality, high integration, and high speed of semiconductor devices, the flip chip connection method (FC connection method) in which conductive protrusions called bumps are formed on semiconductor chips or substrates to directly connect semiconductor chips and substrates is expanding.

[0003] For example, regarding the connection between a semiconductor chip and a substrate, the COB (Chip On Board) type connection method widely 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 (e.g., bumps and wiring) is formed on a semiconductor chip to connect semiconductor chips.

[0004] In addition, in the strong demand for further miniaturization, thinning and high-functionality packaging, chip stacking packaging, POP (Package On Package), TSV (Through-Silicon Via), etc., which use the above-mentioned connection method to stack chips and multi-segment, have also become widely popular. This stacking / multi-segment technology arranges the connection components such as semiconductor chips in three dimensions, so it can reduce the package compared to the method of arranging the connection components in two dimensions. In addition, since it is also effective in improving the performance of semiconductors, reducing noise, reducing the installation area, and saving power, it has attracted much attention as a new era of semiconductor wiring technology.

[0005] However, from the viewpoint of fully ensuring the connection reliability (for example, insulation reliability), metal bonding is usually used when connecting the connecting parts to each other. As the main metals used for the above-mentioned connecting parts (for example, bumps and wiring), there are solder, tin, gold, silver, copper, nickel, etc., and conductive materials containing a variety of these can also be used. Regarding the metal used in the connecting part, surface oxidation leads to the formation of an oxide film, and causes impurities such as oxides to adhere to the surface, and sometimes impurities are generated on the connecting surface of the connecting part. If such impurities remain, the connection reliability (for example, insulation reliability) between the semiconductor chip and the substrate or between two semiconductor chips is reduced, and there is a concern that the advantages of adopting the above-mentioned connection method will be impaired.

[0006] In addition, as a method of suppressing the generation of these impurities, there is a method of coating the connection portion with an oxidation-resistant film known as OSP (Organic Solderability Preservatives) treatment, but the oxidation-resistant film may cause a decrease in solder wettability and connectivity during the connection process.

[0007] Therefore, as methods for removing the above-mentioned oxide film and impurities, there have been proposed methods using a single-layer film containing a flux in a semiconductor material (for example, refer to Patent Document 1), a method using a double-layer film consisting of a thermosetting resin layer and a thermoplastic resin layer containing an acid component (for example, refer to Patent Document 2), and the like.

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: International Publication No. 2013 / 125086

[0011] Patent Document 2: International Publication No. 2016 / 117350 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] An object of one aspect of the present invention is to provide a film-like adhesive for a semiconductor that can suppress the amount of fillet generated while ensuring sufficient sealing properties.

[0014] Means for solving technical problems

[0015] The present invention provides the following [1] to

[15] . [1]

[0017] A film-like adhesive for semiconductors, comprising a first adhesive region not containing a flux compound and a second adhesive region containing a flux compound along a thickness direction,

[0018] The first adhesive region comprises a first epoxy resin, a first imidazole curing agent and a (meth) acrylic compound,

[0019] The second adhesive region includes a second epoxy resin, a second imidazole curing agent and the flux compound. [2]

[0021] The film-like adhesive for semiconductor according to [1], wherein

[0022] The first adhesive region does not contain a radical polymerization initiator. [3]

[0024] The film-like adhesive for semiconductor according to [1] or [2], wherein:

[0025] At least one of the first epoxy resin and the second epoxy resin includes an epoxy resin that is liquid at 25°C. [4]

[0027] The film-like adhesive for semiconductor according to any one of [1] to [3], wherein

[0028] At least one of the first epoxy resin and the second epoxy resin includes a trisphenol methane epoxy resin. [5]

[0030] The film-like adhesive for semiconductor according to any one of [1] to [4], wherein

[0031] At least one of the first imidazole-based curing agent and the second imidazole-based curing agent has a triazine ring. [6]

[0033] The film-like adhesive for semiconductor according to any one of [1] to [5], wherein

[0034] The ratio of the content of the first epoxy resin in the first adhesive region to the content of the (meth)acrylic compound is 3 to 11 in terms of mass ratio. [7]

[0036] The film-like adhesive for semiconductor according to any one of [1] to [6], wherein

[0037] The (meth)acrylic compound includes a multifunctional (meth)acrylic compound having 2 to 8 (meth)acryloyl groups. [8]

[0039] The film-like adhesive for semiconductor according to any one of [1] to [7], wherein

[0040] The flux compound comprises a polycarboxylic acid. [9]

[0042] The film-like adhesive for semiconductor according to any one of [1] to [8], wherein

[0043] The thickness of the first adhesive region is 1 to 50 μm,

[0044] The thickness of the second adhesive region is 0.5 to 2 times the thickness of the first adhesive region.

[10]

[0046] The film-like adhesive for semiconductor according to any one of [1] to [9], which is non-conductive.

[11]

[0048] The film-like adhesive for semiconductor according to any one of [1] to

[10] is used to bond a semiconductor chip and a substrate and seal a gap between the semiconductor chip and the substrate.

[12]

[0050] A method for producing a film-like adhesive for a semiconductor, which is the method for producing a film-like adhesive for a semiconductor according to any one of [1] to

[11] , comprising the step of providing one of a first adhesive layer and a second adhesive layer on the other,

[0051] The first adhesive layer is a layer including the first epoxy resin, the first imidazole curing agent, and the (meth)acrylic compound but not including a flux compound.

[0052] The second adhesive layer is a layer including the second epoxy resin, the second imidazole-based curing agent, and the flux compound.

[13]

[0054] An adhesive tape comprising:

[0055] The film adhesive for semiconductor according to any one of [1] to

[11] ; and

[0056] The back grinding tape is provided on the film-like adhesive for semiconductor and on the side opposite to the first adhesive region side when viewed from the second adhesive region.

[14]

[0058] A method for manufacturing a semiconductor device, comprising:

[0059] A step of preparing a semiconductor chip with a film-like adhesive, the semiconductor chip with a film-like adhesive comprising: a semiconductor chip, and the film-like adhesive for semiconductor described in any one of [1] to

[11] , which is arranged on the semiconductor chip in such a manner that a surface of the first adhesive region on the side opposite to the second adhesive region faces the semiconductor chip; and

[0060] The semiconductor chip with the film adhesive is placed on a substrate from the film adhesive side and heated to electrically connect a connection portion of the semiconductor chip and a connection portion of the substrate and seal a gap between the semiconductor chip and the substrate.

[15]

[0062] A semiconductor device comprising: a semiconductor chip having a first connection portion; a substrate having a second connection portion electrically connected to the first connection portion; and a sealing portion that joins the semiconductor chip and the substrate and fills a gap between the semiconductor chip and the substrate.

[0063] The sealing portion is a cured product of the film-like adhesive for a semiconductor according to any one of [1] to

[11] .

[0064] Effects of the Invention

[0065] According to the present invention, it is possible to provide a film-like adhesive for a semiconductor that can suppress the amount of fillet generated while ensuring sufficient sealing properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a schematic cross-sectional view showing one embodiment of the film-like adhesive for semiconductor of the present invention.

[0067] Figure 2 (a) is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention, Figure 2 (b) is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

[0068] Figure 3 This is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

[0069] Figure 4 The present invention is a cross-sectional view schematically showing a process of one embodiment of a method for manufacturing a semiconductor device according to the present invention.

[0070] Figure 5 It indicates to continue Figure 4 A process cross-section view of the process.

[0071] Figure 6 It indicates to continue Figure 5A process cross-section view of the process.

[0072] Figure 7 It indicates to continue Figure 6 A process cross-section view of the process.

[0073] Figure 8 It indicates to continue Figure 7 A process cross-section view of the process. DETAILED DESCRIPTION

[0074] In this specification, "(meth)acrylic acid" means at least one of acrylic acid and its corresponding methacrylic acid. The same applies to other similar expressions such as "(meth)acryloyl", "(meth)acrylate", etc. In addition, the numerical range represented by "~" indicates a range that includes the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. In addition, except for specific explicit cases, the units of the numerical values ​​recorded before and after "~" are the same. In addition, in the numerical range described in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. In addition, the upper limit and lower limit values ​​recorded individually can be combined arbitrarily. In addition, unless otherwise specified, the materials exemplified below can be used alone or in combination of two or more. In the case where there are multiple substances that meet the requirements of each component in the composition, unless otherwise specified, the content of each component in the composition represents the total amount of the multiple substances present in the composition.

[0075] Hereinafter, 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 corresponding parts are marked with the same symbols, and repeated descriptions are omitted. Furthermore, regarding positional relationships such as up, down, left, and right, unless otherwise specified, the positional relationships shown in the accompanying drawings are used as a reference. In addition, the dimensional ratios of the accompanying drawings are not limited to the ratios shown in the drawings.

[0076] <Film Adhesives for Semiconductors>

[0077] A film adhesive for semiconductors (hereinafter referred to as "film adhesive") according to one embodiment is an adhesive used for connecting (bonding) and sealing connecting components such as semiconductor chips, and can be used to bond semiconductor chips and substrates and seal gaps between the semiconductor chips and substrates.

[0078] Figure 1 1 is a schematic cross-sectional view showing a film adhesive according to one embodiment. The film adhesive 1 shown in the figure is Figure 1In the vertical direction), there is a first adhesive region 2 that does not contain a flux compound and a second adhesive region 3 that contains a flux compound. The first adhesive region 2 contains an epoxy resin, an imidazole curing agent and a (meth) acrylic compound, and the second adhesive region contains an epoxy resin, an imidazole curing agent and the above-mentioned flux compound. Hereinafter, the adhesive constituting the first adhesive region 2 will be referred to as the first adhesive, and the adhesive constituting the second adhesive region 3 will be referred to as the second adhesive. In addition, the epoxy resin and the imidazole curing agent contained in the first adhesive will be referred to as the first epoxy resin and the first imidazole curing agent, respectively, and the epoxy resin and the imidazole curing agent contained in the second adhesive will be referred to as the second epoxy resin and the second imidazole curing agent, respectively.

[0079] The first adhesive region 2 and the second adhesive region 3 have a predetermined thickness, for example, Figure 1 As shown, along the main surface direction of the film adhesive 1 ( Figure 1 The first adhesive region 2 and the second adhesive region 3 may also be layered. That is, the first adhesive region 2 and the second adhesive region 3 may also be the first adhesive layer and the second adhesive layer, respectively. The boundary between the first adhesive region 2 and the second adhesive region 3 may not be clear and may be difficult to visually distinguish. Figure 1 In the embodiment, the first adhesive region 2 and the second adhesive region 3 are adjacent to each other, but between the first adhesive region 2 and the second adhesive region 3, there may also be a region different from the first adhesive region 2 and the second adhesive region 3 (for example, a region including a mixture of the first adhesive and the second adhesive).

[0080] However, in recent years, as the gaps between layers and the spacing between wirings have become narrower with the high functionality and high integration of packages, the flowing adhesive during connection has become easy to overflow from the end of the connecting component (for example, a semiconductor chip), and has become easy to form an overflow portion called a fillet. This fillet can cause damage to the connecting component, so it is required to develop a method to reduce the amount of fillets while ensuring sufficient sealing. In the case of using only an adhesive with low fluidity to suppress fillets, the connecting parts of the connecting components are not fully filled with the adhesive, which sometimes causes undesirable conditions such as gaps. Therefore, it is not easy to solve the above problems by simply reducing the fluidity of the adhesive.

[0081] On the other hand, the inventors of the present invention have found that, as a result of research, the above-mentioned film-like adhesive can ensure sufficient sealing performance while suppressing the generation of gaps when connecting the connecting parts and the generation of rounded corners caused by excessive flow of the adhesive. Although the reason for exerting this effect is still uncertain, from the aspect that the first adhesive region 2 and the second adhesive region 3 have the above-mentioned specific composition, it is speculated that the reasons are as follows: the first adhesive region 2 has appropriate fluidity that is difficult to produce unfilled parts that cause gaps when attached, and solidifies faster than the second adhesive region 3 during connection and is difficult to produce excessive flow that causes rounded corners; and the second adhesive region 3 is easier to flow than the first adhesive region 2 and is difficult to produce unsealed parts.

[0082] The thickness of the first adhesive region 2 (the length in the thickness direction of the film adhesive 1) can be appropriately set according to the relationship with the height of the connecting portion in the connecting component to which the film adhesive 1 is attached. If the height of the connecting portion is set to y1 and the thickness of the first adhesive region 2 is set to x1, from the viewpoint that the cured product of the first adhesive becomes difficult to intervene between the connecting portions and the connection reliability can be further improved, x1<y1 or 1.0x1<y1≤1.5x1 can be set. Specifically, the thickness of the first adhesive region 2 can be 1 to 50 μm, or 3 to 50 μm, 4 to 30 μm, or 5 to 20 μm.

[0083] The thickness of the second adhesive region 3 may be 0.5 to 2 times, 0.5 to 2.5 times, or 0.5 to 3 times the thickness of the first adhesive region 2. Specifically, the thickness of the second adhesive region 3 (the length in the thickness direction of the film adhesive 1) may be 1 to 50 μm, 3 to 50 μm, 4 to 30 μm, or 5 to 20 μm.

[0084] The thickness of the film adhesive 1 (for example, the sum of the thickness of the first adhesive region 2 and the thickness of the second adhesive region 3) can be appropriately set according to the relationship with the connection portion of the connecting component. When the sum of the heights of the connection portions is set to x and the total thickness of the film adhesive is set to y, from the viewpoint of the connectivity during crimping and the filling property of the adhesive, it can be 0.70x≤y≤1.3x, or it can be 0.80x≤y≤1.2x. From the viewpoint that it becomes difficult for the cured product of the first adhesive to intervene between the connection portions and the connection reliability is further improved, y>x can be satisfied. Specifically, the thickness of the film adhesive 1 can be 2 to 100 μm, or it can be 6 to 100 μm, 8 to 60 μm, or 10 to 40 μm.

[0085] Hereinafter, the first adhesive constituting the first adhesive region 2 and the second adhesive constituting the second adhesive region 3 will be described.

[0086] (1st adhesive)

[0087] The first adhesive includes a first epoxy resin, a first imidazole curing agent, and a (meth) acrylic compound, and does not include a flux compound. Here, the first adhesive does not include a flux compound, which means that the content of the flux compound in the first adhesive is below the current detection limit (for example, 0.01% by mass or less based on the total amount of the first adhesive).

[0088] [First Epoxy Resin]

[0089] The first epoxy resin is a compound having more than two epoxy groups in the molecule. As the first epoxy resin, for example, 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, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin and various multifunctional epoxy resins can be used. These can be used alone or as a mixture of more than two kinds. Among these, when using trisphenol methane type epoxy resin (epoxy resin containing trisphenol methane skeleton), the amount of fillet generation tends to be further reduced.

[0090] From the viewpoint of suppressing the generation of volatile components due to decomposition during connection at high temperature, the first epoxy resin may have a weight loss rate of 5% or less at the temperature during connection. For example, when the temperature during connection is 250° C., an epoxy resin having a weight loss rate of 5% or less at 250° C. may be used. Also, when the temperature during connection is 300° C., an epoxy resin having a weight loss rate of 5% or less at 300° C. may be used.

[0091] As the first epoxy resin, from the viewpoint of easily suppressing the occurrence of cracks and fissures on the film surface, an epoxy resin that is liquid at 25°C (hereinafter referred to as "liquid epoxy resin") may be used. Here, "liquid at 25°C" means that the viscosity at 25°C measured by an E-type viscometer is 400 Pa·s or less. Examples of the liquid epoxy resin include bisphenol A glycidyl ether, bisphenol AD ​​glycidyl ether, bisphenol S glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol A glycidyl ether, ethylene oxide adduct bisphenol A glycidyl ether, propylene oxide adduct bisphenol A glycidyl ether, glycidyl ether of naphthalene resin, trifunctional or tetrafunctional glycidyl amine, and the like.

[0092] From the viewpoint of easily suppressing the occurrence of cracks and fissures on the film surface, the content of the liquid epoxy resin in the first adhesive may be 5% by mass or more, 10% by mass or more, or 20% by mass or more, based on the total amount of the first epoxy resin contained in the first adhesive. From the viewpoint of easily suppressing the excessive increase in the viscosity of the film and easily suppressing the edge fusion, the content of the liquid epoxy resin may be 30% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total amount of the first epoxy resin.

[0093] The epoxy equivalent of the first epoxy resin may be 100 to 3000 g / eq, 100 to 2000 g / eq, or 100 to 1500 g / eq. When the epoxy equivalent of the first epoxy resin is within the above range, the balance between reactivity and fluidity during heating is likely to be good.

[0094] From the viewpoint of easily suppressing the generation of rounded corners, the content of the first epoxy resin in the first adhesive may be 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the first adhesive. From the viewpoint of easily obtaining good sealing properties and easily suppressing the generation of voids, the content of the first epoxy resin may be 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total amount of the first adhesive.

[0095] The content of the first epoxy resin in the first adhesive can also be set according to the relationship with the content of the above-mentioned (meth) acrylic compound. If the ratio of the content of the first epoxy resin in the first adhesive to the content of the (meth) acrylic compound is 3 to 11 in terms of mass ratio, it tends to be easy to obtain high connection reliability, and the amount of fillet generation is further reduced. From the viewpoint of further reducing the amount of fillet generation, the above-mentioned ratio can also be 5 or more, 7 or more, or 9 or more. In addition to the above-mentioned effects, from the perspective of easily obtaining good sealing properties and easily suppressing the generation of voids, it can also be 10 or less.

[0096] [No. 1 Imidazole Curing Agent]

[0097] 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'-undecyl imidazole-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazol-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazol-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and epoxy resin and imidazole adduct. In addition, latent curing agents that microencapsulate these can also be used. These can be used alone or in combination with two or more. Among these, from the viewpoint of easily obtaining better sealing properties and the viewpoint of easily suppressing the generation of voids, compounds with triazine rings can be used.

[0098] From the viewpoint of improving curability during heating, the content of the first imidazole curing agent in the first adhesive may be 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, relative to 100 parts by mass of the first epoxy resin contained in the first adhesive. From the viewpoint of making it more difficult for the first adhesive to intervene between the connecting parts, the content of the first imidazole curing agent may be 10 parts by mass or less, 7 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the first epoxy resin.

[0099] [(Meth)acrylic acid compound]

[0100] (Meth) acrylic acid compounds are compounds having one or more (meth) acryloyl groups in the molecule. As (meth) acrylic acid compounds, for example, (meth) acrylic acid compounds containing skeletons of bisphenol A type, bisphenol F type, naphthalene type, phenol novolac type, cresol novolac type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type, adamantane type or isocyanuric acid type can be used; various multifunctional (meth) acrylic acid compounds (excluding (meth) acrylic acid compounds containing the skeletons) and the like. As multifunctional (meth) acrylic acid compounds, pentaerythritol tri(meth) acrylate, dipentaerythritol poly(meth) acrylate (dipentaerythritol penta(meth) acrylate, dipentaerythritol hexa(meth) acrylate, etc.), trimethylolpropane di(meth) acrylate and the like can be cited. Among these, when a multifunctional (meth)acrylic compound is used, the effect of the present invention tends to be further improved, and when a dipentaerythritol poly(meth)acrylate is used, the effect of the present invention tends to be further improved. The number of functional groups (the number of (meth)acryloyl groups) of the multifunctional (meth)acrylic compound may be 2 to 8, 3 to 7, or 4 to 6.

[0101] The molecular weight of the (meth)acrylic compound is, for example, 400 to 2000. The molecular weight of the (meth)acrylic compound may be less than 2000 or less than 1000. The smaller the molecular weight of the (meth)acrylic compound, the easier it is to react, and the higher the curing reaction rate.

[0102] The (meth)acrylic acid compound can be used alone or in combination of two or more.

[0103] From the viewpoint of further reducing the amount of fillets generated, the content of the (meth) acrylic compound in the first adhesive may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total amount of the first adhesive. From the viewpoint of improving the sealing performance and suppressing the generation of voids, the content of the (meth) acrylic compound may be 10% by mass or less, 7% by mass or less, or 5% by mass or less, based on the total amount of the first adhesive. From these viewpoints, the content of the (meth) acrylic compound may be 1-10% by mass, 3-7% by mass, or 3-5% by mass, based on the total amount of the first adhesive.

[0104] [Other ingredients]

[0105] The first adhesive may further contain components other than the above components (other components).

[0106] For example, the first adhesive may also contain a thermosetting resin other than epoxy resin (a compound that is cured by reacting with a thermosetting agent using heat). Examples of thermosetting resins other than epoxy resin include phenolic resins and acrylic resins. When the first adhesive contains a thermosetting resin other than epoxy resin, the content of the first epoxy resin in the first adhesive may be 80% by mass or more, 90% by mass or more, or 100% by mass, based on the total amount of the thermosetting resin contained in the first adhesive.

[0107] Furthermore, for example, the first adhesive may also contain a thermosetting agent other than the imidazole curing agent. Examples of thermosetting agents other than the imidazole curing agent include phenolic resin curing agents, acid anhydride curing agents, amine curing agents, and phosphine curing agents. When the first adhesive contains a thermosetting agent other than the imidazole curing agent, the content of the first imidazole curing agent in the first adhesive may be 80% by mass or more, 90% by mass or more, or 100% by mass, based on the total amount of the thermosetting agent contained in the first adhesive, from the viewpoint that the first imidazole curing agent can be cured quickly when heated at low temperatures and the connection reliability can be improved by suppressing the flux activity that generates an oxide film at the connection portion.

[0108] Furthermore, for example, the first adhesive may also contain a radical polymerizable compound other than the (meth)acrylic compound (a compound capable of undergoing a radical polymerization reaction by generating radicals by heat, light, radiation, electrochemical action, etc.). Examples of the radical polymerizable compound other than the (meth)acrylic compound include vinyl compounds and the like. When the first adhesive contains a radical polymerizable compound other than the (meth)acrylic compound, the content of the (meth)acrylic compound in the first adhesive may be 80% by mass or more, 90% by mass or more, or 100% by mass, based on the total amount of the radical polymerizable compound contained in the first adhesive.

[0109] And, for example, the first adhesive may also contain a thermoplastic resin. Thermoplastic resins contribute to the improvement of heat resistance and the improvement of film formation. As thermoplastic resins, for example, phenoxy resins, polyimide resins, polyamide resins, polycarbodiimide resins, cyanate resins, acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, carbamate resins and acrylate rubbers can be cited. Among these, from the viewpoint of easily obtaining excellent heat resistance and film formation, it can be any one of phenoxy resins, polyimide resins, acrylate rubbers, cyanate resins and polycarbodiimide resins, and from the viewpoint of easily further obtaining excellent heat resistance and film formation, it can be any one of phenoxy resins, polyimide resins and acrylate rubbers. These thermoplastic resins can also be used alone or as a mixture or copolymer of two or more.

[0110] The weight average molecular weight of the thermoplastic resin is, for example, more than 10,000, or more than 20,000 or more than 30,000. According to this thermoplastic resin, the heat resistance and film forming property of the first adhesive can be further improved. From the viewpoint of easily obtaining the effect of improving heat resistance, the weight average molecular weight of the thermoplastic resin can be less than 1,000,000, or less than 500,000. In addition, in this specification, the weight average molecular weight represents the weight average molecular weight when measured in terms of polystyrene using a high performance liquid chromatograph (manufactured by SHIMADZU CORPORATION, product name: C-R4A). When measuring, for example, the following conditions can be used.

[0111] Detector: LV4000 UV Detector (manufactured by Hitachi, Ltd., product name)

[0112] Pump: L6000 Pump (manufactured by Hitachi, Ltd., product name)

[0113] Column: Gelpack GL-S300MDT-5 (2 pieces in total) (manufactured by Hitachi Chemical Co., Ltd., product name)

[0114] Eluent: THF / DMF=1 / 1 (volume ratio)+LiBr(0.03mol / L)+H3PO4(0.06mol / L)

[0115] Flow rate: 1mL / min

[0116] From the viewpoint of excellent adhesion of the film adhesive 1 to the connection member (e.g., semiconductor chip), the glass transition temperature (Tg) of the thermoplastic resin may be 120° C. or lower, 100° C. or lower, or 85° C. or lower. The Tg is measured using DSC (manufactured by PerkinElmer Co., Ltd., product name: DSC-7 model) under the conditions of a sample amount of 10 mg, a heating rate of 10° C. / min, and a measurement atmosphere of air.

[0117] From the viewpoint of easily improving the heat resistance and film forming property of the first adhesive, the content of the thermoplastic resin in the first adhesive may be 5% by mass or more, 7% by mass or more, or 10% by mass or more, based on the total amount of the first adhesive. From the viewpoint of easily suppressing the generation of rounded corners, the content of the thermoplastic resin may be 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of the first adhesive.

[0118] Furthermore, for example, the first adhesive may also contain a filler (filler). The filler is effective in controlling the viscosity of the first adhesive, the physical properties of the cured product of the first adhesive, and the like. Specifically, by using a filler, it is possible to suppress the generation of voids during connection, reduce the moisture absorption rate of the cured product of the first adhesive, and the like. The filler may be an inorganic filler (inorganic particles) or an organic filler (organic particles). As an inorganic filler, insulating inorganic fillers such as glass, silica, alumina, titanium oxide, mica, and boron nitride may be cited. Among these, when at least one selected from the group consisting of silica, alumina, titanium oxide, and boron nitride is used, the above-mentioned effect is easily obtained, and when at least one selected from the group consisting of silica, alumina, and boron nitride is used, the above-mentioned effect is more easily obtained. As an organic filler, for example, a resin filler (resin particles) may be cited. As a resin filler, polyurethane, polyimide, and the like may be cited. According to the resin filler, flexibility at high temperatures such as 260°C can be imparted. In addition, an organic filler composed of a thermoplastic resin does not correspond to the above-mentioned thermoplastic resin.

[0119] From the viewpoint of further improving insulation reliability, the filler may be insulating. The first adhesive may not contain a filler (conductive filler) made of a conductive material such as silver, solder, or carbon black.

[0120] The physical properties of the filler can also be appropriately adjusted by surface treatment. From the viewpoint of improving dispersibility or adhesion, the filler can be a filler that has been surface treated. As the surface treatment agent, glycidol (epoxy), amine, phenyl, phenylamine, (meth) acrylic acid, vinyl compounds, etc. can be cited.

[0121] The average particle size of the filler is, for example, 0.5 to 1.5 μm. From the viewpoint of preventing biting during flip chip connection, the average particle size of the filler may be 1.5 μm or less, and from the viewpoint of excellent visual discernibility (transparency), it may be 1.0 μm or less. In addition, the average particle size of the filler is the particle size corresponding to the point of 50% volume when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles as 100%, and can be measured by a particle size distribution measuring device using a laser diffraction scattering method, etc.

[0122] From the viewpoint of suppressing the decrease of heat dissipation and facilitating the suppression of the generation of voids and the increase of moisture absorption rate, the content of the filler in the first adhesive may be 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the first adhesive. From the viewpoint of suppressing the occurrence of filler biting (capturing) in the connecting portion, the content of the filler may be 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the total amount of the first adhesive.

[0123] When the filler includes an inorganic filler and an organic filler, the content of the inorganic filler in the first adhesive may be 60 mass % or more, 70 mass % or more, or 80 mass % or more, based on the total amount of the filler contained in the first adhesive, or may be 98 mass % or less, 95 mass % or less, or 90 mass % or less, or may be 60-98 mass %, 70-95 mass % or 80-90 mass %.

[0124] Furthermore, for example, the first adhesive may contain a radical polymerization initiator. The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator.

[0125] The photoradical polymerization initiator is, for example, a compound that decomposes and generates free radicals by irradiation with light having a wavelength in the range of 150 to 750 nm (for example, ultraviolet light), and examples thereof include known photopolymerization initiators having structures such as an oxime ester structure, a bisimidazole structure, an acridine structure, an α-aminoalkylphenone structure, an aminobenzophenone structure, an N-phenylglycine structure, an acylphosphine oxide structure, a benzyldimethylketal structure, an α-hydroxyalkylphenone structure, and an α-hydroxyacetophenone structure.

[0126] Examples of the thermal radical polymerization initiator include 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di(4-tert-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, cumyl peroxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 、2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneoheptanoate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, tert-amyl peroxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, di(3-methylbenzoyl)peroxide, Dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di(3-methylbenzoylperoxy)hexane, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, tert-butyl peroxybenzoate , dibutyl peroxytrimethyladipate, tert-amyl peroxyoctanoate, tert-amyl peroxyisononanoate, tert-amyl peroxybenzoate and other organic peroxides; azo compounds such as 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid) and 1,1'-azobis(1-cyclohexanecarbonitrile), etc.

[0127] From the viewpoint of further improving the effects of suppressing rounded corners, reducing voids, and improving sealing properties, the content of the free radical polymerization initiator in the first adhesive may be less than 0.1 parts by mass, or may be less than 0.01 parts by mass, relative to 100 parts by mass of the (meth) acrylic acid compound contained in the first adhesive. From the same viewpoint, the first adhesive may not contain a free radical polymerization initiator. Here, the first adhesive not containing a free radical polymerization initiator means that the content of the free radical polymerization initiator in the first adhesive is below the current detection limit (for example, less than 0.01% by mass based on the total amount of the first adhesive).

[0128] The first adhesive may further contain additives such as an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trapping agent. These can be used alone or in combination of two or more. The contents of these additives can be appropriately adjusted to show the effects of each additive.

[0129] (Second adhesive)

[0130] The second adhesive includes a second epoxy resin, a second imidazole curing agent and a flux compound.

[0131] [Second epoxy resin and second imidazole curing agent]

[0132] As the second epoxy resin and the second imidazole thermosetting agent, the same compounds as those exemplified as the first epoxy resin and the first imidazole curing agent can be used, and the preferred embodiments thereof are also the same. The first epoxy resin and the second epoxy resin may be the same or different. The first imidazole curing agent and the second imidazole curing agent may be the same or different.

[0133] From the viewpoint of easily suppressing the generation of rounded corners, the content of the second epoxy resin in the second adhesive may be 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the second adhesive. From the viewpoint of easily obtaining good sealing and adhesion, the content of the second epoxy resin may be 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total amount of the second adhesive.

[0134] From the viewpoint of improving curability during heating, the content of the second imidazole curing agent in the second adhesive may be 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, relative to 100 parts by mass of the second epoxy resin contained in the second adhesive. From the viewpoint of making it difficult for the second adhesive to further intervene between the connecting parts, the content of the second imidazole curing agent may be 10 parts by mass or less, 7 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the second epoxy resin contained in the second adhesive.

[0135] [Flux Compounds]

[0136] The flux compound is a compound having flux activity. As the flux compound, any known compound can be used without particular limitation as long as it is a compound that reduces and removes the oxide film on the surface of solder or the like to facilitate metal bonding. The flux compound can be used alone or in combination of two or more.

[0137] From the viewpoint of obtaining sufficient flux activity and obtaining more excellent connection reliability, the flux compound can be a compound (carboxylic acid) having a carboxyl group, or a polycarboxylic acid having more than two carboxyl groups. Compared with a compound (monocarboxylic acid) having one carboxyl group, a polycarboxylic acid is difficult to volatilize by the high temperature during connection, so the generation of voids can be further suppressed by using a polycarboxylic acid. Moreover, among polycarboxylic acids, compared with polycarboxylic acids having more than three carboxyl groups, polycarboxylic acids having two carboxyl groups have excellent effects in suppressing the viscosity increase of the film adhesive 1 during storage / connection operation, etc.

[0138] The flux compound having a carboxyl group may be a compound having a group represented by the following formula (1).

[0139]

[0140] In formula (1), R 1 represents a hydrogen atom or an electron-donating group.

[0141] From the perspective of excellent reflow resistance and further excellent connection reliability, R 1 In this embodiment, the second binder contains an epoxy resin and may further contain a compound having a group represented by formula (1) wherein R 1 In this case, even in the flip chip connection method, it is easy to manufacture a semiconductor device with better reflow resistance and connection reliability.

[0142] Examples of the electron donating group include alkyl, hydroxyl, amino, alkoxy, and alkylamino groups. The electron donating group may be a group that does not readily react with other components (eg, epoxy resin), and specifically, may be alkyl, hydroxyl, or alkoxy.

[0143] The alkyl group may be straight-chain or branched. The alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms. The more carbon atoms the alkyl group has, the greater the electron donating property and the greater the steric hindrance. The alkyl group having the carbon number within the above range has an excellent balance between the electron donating property and the steric hindrance.

[0144] The flux compound having two carboxyl groups may be a compound represented by the following formula (2): According to the compound represented by the following formula (2), the reflow resistance and connection reliability of the semiconductor device can be further improved.

[0145]

[0146] In formula (2), R 1has the same meaning as in formula (1). 2 represents a hydrogen atom or an electron-donating group, and n represents an integer of 0 or 1 or more.

[0147] By R 2 The electron donating property of R 1 The examples of electron donating groups described above are the same. 2 Can be used with R 1 Same as R 1 Different. There are multiple R 2 They can be the same as each other or different.

[0148] n in formula (2) may be 1 or more. If n is 1 or more, the flux compound is less likely to volatilize even at high temperatures during connection, compared to when n is 0, thereby further suppressing the generation of voids. In addition, n in formula (2) may be 15 or less, or 11 or less, 6 or less, or 4 or less. If n is 15 or less, better connection reliability may be obtained.

[0149] Specific examples of the flux compound as described above include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid, and compounds in which the second position of these dicarboxylic acids is substituted with an electron-donating group (e.g., 2-methylglutaric acid), etc. Among these, when 2-methylglutaric acid is used, there is a tendency to improve the effects of suppressing rounding, reducing voids, and improving sealing properties by combining an epoxy resin and an imidazole-based curing agent.

[0150] The melting point of the flux compound may be below 150°C, below 140°C or below 130°C. This flux compound is easy to fully exhibit flux activity before the curing reaction of the epoxy resin and the imidazole curing agent occurs. Therefore, by using this flux compound, a semiconductor device with better connection reliability can be obtained. The flux compound may be solid at room temperature (25°C). The melting point of the flux compound may be above 25°C, or above 50°C. In addition, in this specification, a melting point of below 150°C means that the upper limit of the melting point is below 150°C, and a melting point of above 25°C means that the lower limit of the melting point is above 25°C.

[0151] From the viewpoint of obtaining a better flux effect, the content of the flux compound in the second binder may be 0.1 mass % or more, 0.3 mass % or more, or 0.5 mass % or more, based on the total amount of the second binder. From the viewpoint of reducing the amount of warpage of a wafer when manufacturing a semiconductor device, the content of the flux compound may be 5 mass % or less, 3 mass % or less, or 2 mass % or less, based on the total amount of the second binder.

[0152] [Other ingredients]

[0153] The second adhesive may also contain the components exemplified as other components that may be contained in the first adhesive. The thermoplastic resin in the first adhesive may be the same as or different from the thermoplastic resin in the second adhesive. The same also applies to other components such as fillers.

[0154] From the viewpoint of easily improving the heat resistance and film forming property of the second adhesive, the content of the thermoplastic resin in the second adhesive may be 5% by mass or more, 7% by mass or more, or 10% by mass or more, based on the total amount of the second adhesive. From the viewpoint of easily suppressing the generation of rounded corners, the content of the thermoplastic resin may be 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of the second adhesive.

[0155] From the perspective of suppressing the decrease in heat dissipation and facilitating the generation of voids and the increase in moisture absorption, the content of the filler in the second adhesive may be 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the second adhesive. From the perspective of suppressing the occurrence of filler biting (capturing) in the connecting portion, the content of the filler may be 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the total amount of the second adhesive.

[0156] The content of the radical polymerization initiator in the second binder may be 0.01 parts by mass or less based on the total amount of the second binder. The second binder may not contain the radical polymerization initiator.

[0157] The flux compound contains a compound that reacts with free radicals and a free radical polymerizable compound, so that the curing reaction proceeds rapidly when heated, and a cured product is easily inserted between the connecting parts, so the second adhesive may not contain a free radical polymerizable compound. The content of the free radical polymerizable compound may be 0.5% by mass or less, 0.05% by mass or less, or 0% by mass, based on the total amount of the second adhesive.

[0158] The film-like adhesive 1 may be non-conductive. That is, the film-like adhesive 1 may be a so-called NCF (NonConductive Film).

[0159] The film-like adhesive 1 described above can be provided on the surface of the first adhesive region 2 side (the side opposite to the second adhesive region 3) and / or the surface of the second adhesive region 3 side (the side opposite to the first adhesive region 2) in a state where a substrate such as a support film and a protective film is provided. In the present invention, a laminate having a substrate and a film-like adhesive provided on the substrate is referred to as an adhesive tape.

[0160] As the substrate, the substrate exemplified as the substrate used in the method for manufacturing the film-like adhesive described later can be used, but the substrate provided on the second adhesive region 3 side of the film-like adhesive 1 may be a back grinding tape. That is, another embodiment of the present invention is an adhesive tape (adhesive tape with back grinding tape), which includes the above-mentioned film-like adhesive 1 and a back grinding tape provided on the film-like adhesive 1 and on the side opposite to the first adhesive region 2 side when viewed from the second adhesive region 3.

[0161] The back grinding tape is usually configured such that one main surface side becomes a pressure-sensitive adhesive layer, but in this case, the back grinding tape is provided on the film adhesive 1 in such a manner that the surface on the pressure-sensitive adhesive layer side becomes the film adhesive 1 side (for example, in such a manner that the pressure-sensitive adhesive layer and the film adhesive are in contact). The thickness of the substrate (for example, the thickness of the back grinding tape) can be 20 to 300 μm.

[0162] The adhesive tape may be a laminate of a substrate and a film-like adhesive obtained by a method for manufacturing a film-like adhesive described later, that is, a method of applying a coating liquid on a substrate to form a coating film and drying it, or may be a laminate obtained by attaching a substrate to a film-like adhesive 1 (for example, laminating a film-like adhesive 1 and a substrate). In the case where the substrate is a back grinding tape, if the coating liquid is applied and dried on the pressure-sensitive adhesive layer of the back grinding tape, undesirable conditions such as damage to the pressure-sensitive adhesive layer and component transfer between pressure-sensitive adhesives may occur, so the adhesive tape can be obtained by attaching the back grinding tape to the film-like adhesive 1.

[0163] <Method for producing film adhesive for semiconductor>

[0164] One embodiment of a method for manufacturing a film-like adhesive 1 includes a step of providing one of a first adhesive layer and a second adhesive layer on the other. Here, the first adhesive layer is a layer composed of the first adhesive described above (i.e., a layer containing a first epoxy resin, a first imidazole curing agent, and a (meth) acrylic compound without a flux compound), and forms a first adhesive region 2 in the film-like adhesive 1. The second adhesive layer is a layer composed of the second adhesive described above (i.e., a layer containing a second epoxy resin, a second imidazole curing agent, and a flux compound), and forms a second adhesive region 3 in the film-like adhesive 1.

[0165] In one embodiment, the step may be, for example, a step of laminating a first adhesive film having the first adhesive layer and a second adhesive film having the second adhesive layer. In this embodiment, the method for producing the film-like adhesive 1 may further include a step of preparing the first adhesive film and the second adhesive film.

[0166] The process of preparing the first adhesive film may also include the process of forming the first adhesive layer on a substrate (e.g., a film-shaped substrate). In the case of forming the first adhesive layer on the substrate, for example, first, the first epoxy resin, the first imidazole curing agent, the (meth) acrylic compound, and other components (fillers, thermoplastic resins, additives, etc.) added as needed are added to an organic solvent, and dissolved or dispersed by stirring, mixing, kneading, etc., thereby preparing a coating liquid containing the first adhesive. Thereafter, the coating liquid is applied to the substrate subjected to the demolding treatment using a blade coater, a roller coater, an applicator, etc. to form a coating film, and then the organic solvent is reduced from the coating film by heating. Thus, the first adhesive layer can be formed on the substrate.

[0167] As an organic solvent for preparing a coating solution, an organic solvent having the characteristic of being able to uniformly dissolve or disperse each component can be used. As such an organic solvent, for example, 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 can be cited. These organic solvents can be used alone or in combination of two or more. Regarding stirring, mixing and kneading when preparing a coating solution, for example, a stirrer, a grinding mill, a three-roll mill, a ball mill, a bead mill or a homogenizing disperser can be used for carrying out.

[0168] As the substrate, there is no particular limitation as long as it is a film with heat resistance that can withstand heating conditions when the organic solvent is volatilized, and examples thereof 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 substrate is not limited to a monolayer film composed of these films, but may also be a multilayer film composed of two or more materials. The substrate may also be a film having a release treatment applied to the surface.

[0169] The drying conditions for volatilizing the organic solvent from the coating film on the substrate may be conditions that allow the organic solvent to fully volatilize. Specifically, for example, heating may be performed at 50 to 200° C. for 0.1 to 90 minutes. If there is no effect on the gap or viscosity adjustment after installation, the organic solvent may be removed to 1.5% by mass or less relative to the total amount of the first adhesive.

[0170] The step of preparing the second adhesive film may include the step of forming the second adhesive layer on the substrate. The second adhesive layer can be formed on the substrate by the same method as the method of forming the first adhesive layer, except that the second epoxy resin, the second imidazole curing agent, the flux compound and other components (filler, thermoplastic resin, additive, etc.) added as needed are used.

[0171] Examples of the method for laminating the first adhesive film and the second adhesive film include heat pressing, roll lamination, vacuum lamination, etc. The lamination can be performed under heating conditions of, for example, 30 to 120°C.

[0172] The film-like adhesive 1 can be obtained, for example, by forming one of the first adhesive layer and the second adhesive layer on a substrate and then forming the other of the first adhesive layer and the second adhesive layer on the obtained first adhesive layer or the second adhesive layer. The first adhesive layer and the second adhesive layer can be formed by the above-mentioned method.

[0173] The film adhesive 1 can be obtained by, for example, substantially simultaneously forming the first adhesive and the second adhesive on a substrate. Examples of methods for simultaneously coating the first adhesive and the second adhesive include sequential coating and multilayer coating.

[0174] <Semiconductor devices>

[0175] Next, a semiconductor device manufactured using the film adhesive for a semiconductor according to the above-described embodiment will be described.

[0176] Figure 2 It is a schematic cross-sectional view showing one embodiment of a semiconductor device. Figure 2The semiconductor device 100 shown in (a) has: a semiconductor chip 20 and a substrate 25 facing each other; wiring (first connection part and second connection part) 15 respectively arranged on the facing surfaces of the semiconductor chip 20 and the substrate 25; a connection bump 30 connecting the semiconductor chip 20 and the wiring 15 of the substrate 25 to each other; and a sealing part 40 composed of a cured product of an adhesive (first adhesive and second adhesive) filling the gap between the semiconductor chip 20 and the substrate 25. The semiconductor chip 20 and the substrate 25 are flip-chip connected by the wiring 15 and the connection bump 30. The wiring 15 and the connection bump 30 are sealed by the cured product of the adhesive and isolated from the external environment. The sealing part 40 has an upper part 40a containing a cured product of the first adhesive and a lower part 40b containing a cured product of the second adhesive.

[0177] Figure 2 The semiconductor device 200 shown in (b) has: a semiconductor chip 20 and a substrate 25 facing each other; bumps (first connection part and second connection part) 32 respectively arranged on the facing surfaces of the semiconductor chip 20 and the substrate 25; and a sealing part 40 composed of a cured product of an adhesive (first adhesive and second adhesive) filling the gap between the semiconductor chip 20 and the substrate 25. The semiconductor chip 20 and the substrate 25 are connected to each other by the facing bumps 32 and are flip-chip connected. The bumps 32 are sealed by the cured product of the adhesive and isolated from the external environment. The sealing part 40 has an upper part 40a containing a cured product of the first adhesive and a lower part 40b containing a cured product of the second adhesive.

[0178] The semiconductor chip 20 is not particularly limited, and a semiconductor chip composed of an element semiconductor (composed of the same element such as silicon and germanium) or a semiconductor chip composed of a compound semiconductor such as gallium arsenide and indium phosphide can be used.

[0179] The base 25 is not particularly limited as long as it is used to mount the semiconductor chip 20 , and examples thereof include a semiconductor chip, a semiconductor wafer, and a printed circuit board.

[0180] Examples of semiconductor chips that can be used as the base 25 are the same as the examples of the semiconductor chip 20 described above, and as the base 25 , a semiconductor chip similar to the semiconductor chip 20 can also be used.

[0181] The semiconductor wafer that can be used as the base 25 is not particularly limited, and may have a structure in which a plurality of semiconductor chips exemplified in the above-mentioned semiconductor chip 20 are connected.

[0182] There are no particular restrictions on the wiring circuit substrate that can be used as the base 25, and a circuit substrate having wiring (wiring pattern) 15 formed on the surface of an insulating substrate whose main components are glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, etc. by etching away unnecessary parts of the metal film, a circuit substrate having wiring 15 formed on the surface of the above-mentioned insulating substrate by metal plating, etc., a circuit substrate having wiring 15 formed on the surface of the above-mentioned insulating substrate by printing a conductive material, etc. can be used.

[0183] The connecting parts such as wiring 15 and bump 32 contain gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.), nickel, tin, lead, etc. as main components, and may also contain multiple metals.

[0184] Among the above metals, gold, silver, and copper can be used from the perspective of a package having excellent electrical conductivity and thermal conductivity of the connection portion. From the perspective of a package having reduced costs, inexpensive materials, namely, silver, copper, and solder can be used. When an oxide film is formed on the surface of a metal at room temperature, productivity decreases and costs increase. Therefore, from the perspective of suppressing the formation of an oxide film, gold, silver, copper, and solder can be used.

[0185] For example, a metal layer with gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth and tin-copper), tin, nickel, etc. as main components may be formed by plating on the surface of the wiring 15 and the bump 32. The metal layer may be composed of only a single component or may be composed of multiple components. In addition, the metal layer may be made into a single layer or a structure in which multiple metal layers are stacked.

[0186] The semiconductor device may also be a device in which a plurality of structures (packages) such as those shown in the semiconductor devices 100 and 200 are stacked. In this case, the semiconductor devices 100 and 200 may be electrically connected to each other through bumps and wirings containing gold, silver, copper, solder (main components of which are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.), tin, nickel, etc.

[0187] As a method of stacking a plurality of semiconductor devices, Figure 3 As shown, for example, TSV (Through-Silicon Via: silicon through-hole) technology can be cited. Figure 3In the semiconductor device 500 shown in FIG. 1 , the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 20 via the connection bump 30, thereby the semiconductor chip 20 and the interposer 50 are flip-chip connected. The gap between the semiconductor chip 20 and the interposer 50 is filled with a cured product of an adhesive (a first adhesive and a second adhesive) to form a sealing portion 40. The semiconductor chip 20 is repeatedly stacked on the surface of the semiconductor chip 20 on the opposite side of the interposer 50 via the wiring 15, the connection bump 30 and the sealing portion 40. The wiring 15 on the pattern surface of the front and back of the semiconductor chip 20 is connected to each other through the through electrode 34 filled in the hole that penetrates the inside of the semiconductor chip 20. In addition, as the material of the through electrode 34, copper, aluminum, etc. can be used.

[0188] By using this TSV technology, it is usually possible to obtain a signal from the back side of a semiconductor chip that is not used. In addition, since the through electrode 34 passes vertically through the semiconductor chip 20, the distance between the opposing semiconductor chips 20 and between the semiconductor chip 20 and the interposer 50 can be shortened, and a flexible connection can be made. The semiconductor film adhesive of this embodiment can be used as a semiconductor film adhesive between the opposing semiconductor chips 20 and between the semiconductor chip 20 and the interposer 50 in this TSV technology.

[0189] Furthermore, in a bump forming method with a high degree of freedom such as the area bump chip technology, a semiconductor chip can be directly mounted on a mainboard without an interposer. The film adhesive for semiconductors of this embodiment can also be applied to a case where such a semiconductor chip is directly mounted on a mainboard. In addition, the film adhesive for semiconductors of this embodiment can also be applied to sealing a gap (void) between two wiring circuit substrates when two wiring circuit substrates are stacked.

[0190] <Method for manufacturing semiconductor device>

[0191] Next, a method for manufacturing a semiconductor device using the film adhesive for a semiconductor according to the above-described embodiment will be described.

[0192] A method for manufacturing a semiconductor device according to an embodiment includes, for example, a step of preparing a semiconductor chip with a film-like adhesive, wherein the semiconductor chip with a film-like adhesive includes: a semiconductor chip, and a film-like adhesive for semiconductor according to the above embodiment, which is arranged on the semiconductor chip in such a manner that the surface of the first adhesive region opposite to the second adhesive region faces the semiconductor chip side; and a step of arranging the semiconductor chip with the film-like adhesive on a substrate from the film-like adhesive side and heating it, thereby electrically connecting the connection portion of the semiconductor chip and the connection portion of the substrate, and sealing the gap between the semiconductor chip and the substrate. The method for manufacturing a semiconductor device may further include a step of attaching the film-like adhesive for semiconductor according to the above embodiment to the connection surface of the semiconductor chip or its precursor from the first adhesive region side. Here, the precursor of the semiconductor chip refers to a component that becomes a semiconductor chip through processing. A specific example of the precursor of the semiconductor chip is a semiconductor wafer. In the case where a semiconductor wafer is used as a precursor of the semiconductor chip, the method for manufacturing a semiconductor device may further include a step of dicing the semiconductor wafer or the semiconductor wafer with the film-like adhesive.

[0193] In the method for manufacturing a semiconductor device, the adhesive tape with the back grinding tape may also be used. In this case, the method for manufacturing a semiconductor device may further include: a lamination step of attaching the adhesive tape with the back grinding tape to the connection surface of the semiconductor wafer, which is the precursor of the semiconductor chip, from the film-like adhesive side for semiconductors; and a back grinding step of grinding the semiconductor wafer to which the adhesive tape is attached, from the side opposite to the adhesive tape.

[0194] Hereinafter, a method of manufacturing a semiconductor device will be described in more detail by taking a method using a precursor of a semiconductor chip (semiconductor wafer) as an example.

[0195] Figures 4 to 8 The following are cross-sectional views schematically showing the steps of one embodiment of a method for manufacturing a semiconductor device. The manufacturing method of one embodiment includes the following steps (a) to (e).

[0196] Step (a): a step of preparing a laminated body 6, the laminated body 6 comprising: a semiconductor wafer A having a connecting portion (first connecting portion) 5 on one main surface (connecting surface); and a film adhesive 1 (see Figure 4 . )

[0197] Step (b): Back grinding step of grinding the side of the laminate 6 opposite to the side where the film adhesive 1 is provided (the side of the semiconductor wafer A opposite to the side where the connection portion 5 is provided) (refer to Figure 5 . )

[0198] Step (c): a step of separating the laminate 6 into individual pieces to obtain a semiconductor chip 8 with a film-like adhesive having a connection portion 5 (see Figure 6 . )

[0199] Step (d): A step of picking up the semiconductor chip 8 with the film adhesive from the film adhesive 1a side that has been singulated (see Figure 7 . )

[0200] Step (e): a step of placing the semiconductor chip 8 with the film-like adhesive on the main surface of a substrate 9 having a connecting portion (second connecting portion) 10 on one main surface (connecting surface) from the film-like adhesive 1a side and heating the substrate 9, thereby electrically connecting the connecting portion 5 of the semiconductor chip 8 with the film-like adhesive and the connecting portion 10 of the substrate 9, and sealing the gap between the semiconductor chip 8 and the substrate 9 (refer to Figure 8 . )

[0201] In addition, when using a semiconductor wafer whose thickness is adjusted in advance, step (b) may not be performed.

[0202] (Step (a))

[0203] Step (a) may be a step of preparing the previously produced laminated body 6 or a step of producing the laminated body 6. The laminated body 6 can be produced, for example, by the following method.

[0204] First, an adhesive tape having a substrate 4 provided on the second adhesive region 3 side of a film-like adhesive 1 is prepared and placed on a predetermined device (see Figure 4 (a). The substrate 4 is, for example, a back grinding tape. Next, a semiconductor wafer A having a connection portion 5 (wiring, bump, etc.) on one main surface is prepared, and a film adhesive 1 is attached to the main surface (the surface having the connection portion 5, the connection surface) of the semiconductor wafer A. Thus, a laminated body 6 (see FIG. 1 ) in which the semiconductor wafer A, the first adhesive region 2, and the second adhesive region 3 are sequentially laminated is obtained. Figure 4 (b). ).

[0205] The film adhesive 1 can be attached by heat pressing, roll lamination, vacuum lamination, etc. The supply area and thickness of the film adhesive 1 are appropriately set according to the size of the semiconductor wafer and the substrate, the height of the connection part, etc. Figure 4 In the embodiment, although the thickness of the film adhesive 1 is greater than the height of the connection portion 5 of the semiconductor wafer A and the connection portion 5 is covered by the film adhesive 1 , the thickness of the film adhesive 1 may be smaller than the height of the connection portion 5 .

[0206] (Step (b))

[0207] In step (b), for example, the semiconductor wafer A of the stacked body 6 is ground using a grinder G (see Figure 5 (a) and Figure 5 (b). Thus, the semiconductor wafer A is thinned. The thickness of the ground semiconductor wafer may be, for example, 10 μm to 300 μm. From the viewpoint of miniaturization and thinning of semiconductor devices, the thickness of the semiconductor wafer may be 20 μm to 100 μm.

[0208] (Step (c))

[0209] In step (c), for example, first, a dicing tape 7 is attached to the semiconductor wafer A side of the stacked body 6, and the stacked body 6 is placed in a predetermined device (see Figure 6 (a). The substrate 4 may be peeled off before or after the laminate 6 is attached to the dicing tape 7. Next, the laminate 6 is cut by a dicing saw D. In this way, the laminate 6 is singulated to obtain semiconductor chips 8 with film adhesives 1a on the semiconductor chips A' (see FIG. Figure 6 (b). A connection portion 5 is provided on the surface of the semiconductor chip A' on the film adhesive 1a side. The film adhesive 1a has a first adhesive region (region formed by the first adhesive) 2a and a second adhesive region (region formed by the second adhesive) 3a.

[0210] (Step (d))

[0211] In step (d), for example, by expanding (dividing) the dicing tape 7, the semiconductor chips 8 with the film adhesive obtained by the above-mentioned dicing are separated from each other, and at the same time, the semiconductor chips with the film adhesive 8 pushed up from the dicing tape 7 side by the needle N are picked up by the pickup tool P from the film adhesive 1a side (refer to Figure 7 The picked-up semiconductor chip 8 with the film-like adhesive is transferred to a bonding tool and used for bonding in step (e).

[0212] (Step (e))

[0213] In step (e), for example, first, a semiconductor chip mounting substrate 9 having a connection portion 10 (second connection portion) on one surface is prepared, and the semiconductor chip 8 with the film adhesive is aligned with the substrate 9. Next, the semiconductor chip 8 with the film adhesive is arranged on the main surface of the substrate 9 provided with the connection portion 10 (wiring, bump, etc.) from the film adhesive 1a side using a bonding tool and heated to bond the semiconductor chip 8 with the film adhesive to the substrate 9 (see FIG. 1 ). Figure 8 (a) and Figure 8(b). Thus, the connection portion 5 of the semiconductor chip 8 with the film-like adhesive is electrically connected to the connection portion 10 of the substrate 9, and a sealing portion 1a' formed by the cured product of the film-like adhesive 1a is formed between the semiconductor chip A' and the substrate 9 to seal the gap between the semiconductor chip 8 and the substrate 9, thereby obtaining a bonded body of the semiconductor chip 8 with the film-like adhesive and the substrate 9, that is, a semiconductor device 11. The sealing portion 1a' has an upper portion 2a' containing a cured product of the first adhesive and a lower portion 3a' containing a cured product of the second adhesive.

[0214] When a solder bump is used for one of the connection portion 5 and the connection portion 10 (for example, when the connection portion 5 or the connection portion 10 is a wiring provided with a solder bump), the connection portion 5 and the connection portion 10 are electrically and mechanically connected by soldering.

[0215] The heating of process (e) can be performed while configuring the semiconductor chip, or it can be performed after configuring the semiconductor chip. The heating and configuration of process (e) can be performed by thermal compression. Process (e) may include: a process of temporarily fixing after position alignment (temporary fixing process); a process of melting the bumps (for example, solder bumps) provided on the connection portion by heat treatment to join the semiconductor chip A' and the substrate 9, and sealing the connection portion (sealing process). In the stage of temporary fixing, since it is not necessary to form a metal bond, the temporary fixing process can be implemented under low load, short time and low temperature. Therefore, when the temporary fixing process and the sealing process are implemented in process (e), productivity can be improved and degradation of the connection portion can be suppressed.

[0216] The load applied for temporary fixation is appropriately set by considering the number of connecting parts (bumps), the absorption of the height deviation of the connecting parts (bumps), the deformation of the connecting parts (bumps), etc. The larger the load, the easier it is to eliminate the gap and make the connecting parts contact. For example, the load near one connecting part (such as a bump) can be 0.009N to 0.2N.

[0217] Regarding the heating in the sealing process, it can be carried out using a device that can heat to a temperature above the melting point of the metal of the connection portion. The heating temperature can be a temperature at which the film adhesive is cured or a temperature at which it is completely cured. The heating temperature and heating time are appropriately set.

[0218] The heating time in the sealing process varies depending on the type of metal constituting the connection portion, but the shorter the heating time, the higher the productivity tends to be. In the case where a solder bump is used for the connection portion, the heating time may be less than 20 seconds, or less than 10 seconds or less than 5 seconds. In the case of copper-copper or copper-gold metal connection, the connection time may be less than 60 seconds.

[0219] In the sealing process, a device capable of heating and pressurizing can also be used to heat and pressurize. That is, the heating in the sealing process can be heating based on thermal compression. In this case, the load (connection load) is set by considering the size of the connecting component, the number of connecting parts, the deviation of the height, the deformation of the connecting part based on the pressurization, etc. The connection load can, for example, exceed the atmospheric pressure and be less than 1MPa. The larger the connection load, the easier it is to suppress the gap and the easier it is to improve the connectivity. On the other hand, the smaller the connection load, the easier it is to suppress the fillet. From these viewpoints, the load can be 0.05 to 0.5MPa. The crimping time (connection time) varies according to the type of metal constituting the connecting part, but there is a tendency that the shorter the crimping time, the higher the productivity. In the case where the connecting part is a solder bump, the crimping time can be less than 20 seconds, or less than 10 seconds or less than 5 seconds. In addition, in the direct pressurization using a crimping machine, the heat of the crimping machine is difficult to transfer to the fillet, so from the point of view that the fillet is easy to fully exert its effect, it can be pressurized by air pressure. From the viewpoint of overall sealing and suppressing rounding, the pressurization during heating may be pressurization by gas pressure (pressurization by a pressurized reflow furnace, a pressurized oven, or the like).

[0220] After the semiconductor chip A′ and the substrate 9 are connected, a heating treatment may be performed in an oven or the like to further improve the connection reliability.

[0221] Example

[0222] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

[0223] The details of the materials used in Examples and Comparative Examples are as follows.

[0224] (Liquid Epoxy Resin)

[0225] ·YX7110B80: Flexible epoxy, manufactured by Mitsubishi Chemical Corporation, product name "jERYX7110B80", "jER" is a registered trademark (the same applies below)

[0226] ·YL983U: Bisphenol F type liquid epoxy, manufactured by Mitsubishi Chemical Corporation, product name "jERYL983U"

[0227] (Solid epoxy resin)

[0228] EP1032: A multifunctional solid epoxy resin containing a trisphenol methane skeleton, manufactured by Mitsubishi Chemical Corporation, product name "jER1032H60"

[0229] (Imidazole curing agent)

[0230] ·2PHZ-PW: 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by SHIKOKU CHEMICALS CORPORATION, product name

[0231] ·2MAOK-PW: 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, manufactured by SHIKOKU CHEMICALS CORPORATION, product name

[0232] (Phenoxy resin)

[0233] ·ZX-1356-2: phenoxy resin, manufactured by Tohto Kasei Co., Ltd., product name, Tg = about 71°C, weight average molecular weight Mw = about 63,000

[0234] (Acrylic acid compound)

[0235] A-DPH: Dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., product name

[0236] (Organic filler)

[0237] EXL-2655: Core-shell organic microparticles, manufactured by Rohm and Haas Company, product name

[0238] (Silica Filler)

[0239] ·KE180G-HLA: Silica filler, manufactured by ADMATECHS COMPANY LIMITED, product name

[0240] (Flux Compound)

[0241] ·2-Methylglutaric acid: manufactured by Sigma-Aldrich Co. LLC, melting point = about 78°C

[0242] <Examples 1 to 7 and Comparative Example 1>

[0243] (Preparation of the first adhesive film)

[0244] The components shown in Table 1 are added to an organic solvent (methyl ethyl ketone) until the NV value ([mass of the coating after drying] / [mass of the coating before drying]×100) becomes 60%, thereby obtaining a mixed solution. At this time, the amount of each component added is set to the amount shown in Table 1 (unit: mass parts). Thereafter, microbeads of Φ1.0 mm and microbeads of Φ2.0 mm are added to the above-mentioned mixed solution, and stirred for 30 minutes using a bead mill (Fritsch Japan Co., Ltd, planetary micro-pulverizer P-7). The amount of microbeads added is set to the same mass as the amount of non-volatile components of the mixed solution (the total amount of components other than the organic solvent). After stirring, the microbeads are removed by filtration. Thus, coating solutions 1A to 8A for forming the first adhesive layer are obtained.

[0245] The obtained coating liquids 1A to 8A were used to obtain the first adhesive films (first adhesive films 1A to 8A) each having the first adhesive layer 1A to 8A. Specifically, first, the coating liquid was applied to a substrate film (manufactured by Teijin Dupont Film Co., Ltd., product name "Purex A54") using a small precision coating device (Yasui Seiki Inc.) so that the film thickness after drying was 4.5 μm. Then, the coating film was dried (80° C. / 10 min) using a clean oven (manufactured by ESPEC), thereby obtaining the first adhesive film having the first adhesive layer.

[0246] [Table 1]

[0247]

[0248] (Preparation of the Second Adhesive Film)

[0249] The components shown in Table 2 were added to an organic solvent (methyl ethyl ketone) so that the NV value became 60%, thereby obtaining a mixed solution. At this time, the amount of each component added was set to the amount shown in Table 2 (unit: mass parts). Thereafter, microbeads of Φ1.0 mm and microbeads of Φ2.0 mm were added to the above-mentioned mixed solution, and stirred for 30 minutes using a bead mill (Fritsch Japan Co., Ltd, planetary micro-crusher P-7). The amount of microbeads added was set to the same mass as the amount of non-volatile components of the mixed solution (the total amount of components other than the organic solvent). After stirring, the microbeads were removed by filtration, thereby obtaining a coating solution 1B and a coating solution 2B for forming a second adhesive layer.

[0250] The obtained coating liquid 1B was applied to a substrate film (manufactured by Teijin Dupont Film Co., Ltd., product name "Purex A54") using a small precision coating device (Yasui Seiki Inc.) so that the film thickness after drying was 4.5 μm. Then, the coating film was dried (80° C. / 10 min) using a clean oven (manufactured by ESPEC), thereby obtaining a second adhesive film 1B having a second adhesive layer 1B. In addition, a second adhesive film 2B having a second adhesive layer 2B was obtained in the same manner except that the coating liquid 2B was used instead of the coating liquid 1B.

[0251] [Table 2]

[0252]

[0253] (Production of film adhesive)

[0254] The first adhesive layer and the second adhesive layer were laminated by laminating any of the first adhesive films 1A to 8A prepared above and the second adhesive film 1B or 2B in the combination shown in Table 3 to prepare film-like adhesives (total thickness 9.0 μm) of Examples 1 to 7 and Comparative Example 1. The lamination temperature was 50°C.

[0255] <Comparative Example 2>

[0256] After obtaining the second adhesive film 1B having the second adhesive layer 1B in the same manner as in the above “Production of the Second Adhesive Film”, two layers of the obtained second adhesive layers 1B were laminated to obtain a film-like adhesive of Comparative Example 2 (total thickness 9.0 μm).

[0257] <Evaluation>

[0258] Using the film adhesives obtained in Examples 1 to 7 and Comparative Examples 1 to 2, connection structures (semiconductor devices) were prepared according to the following procedures. The obtained connection structures were used to evaluate fillet length, gap, and sealing properties by the following methods. The results are shown in Table 3.

[0259] (Production of connection structure)

[0260] The film adhesive obtained in Examples 1 to 7 and Comparative Examples 1 to 2 was cut into a predetermined size (8 mm in length × 8 mm in width × 9.0 μm in thickness) to prepare an evaluation sample. Next, the evaluation sample was attached to the surface (connection surface) of a semiconductor chip with solder bumps (chip size: 7.3 mm in length × 7.3 mm in width × 0.15 mm in thickness, bump height: copper pillar + solder totaling approximately 40 μm, number of bumps 328) on which the solder bumps were provided, to obtain a laminate of the evaluation sample and the semiconductor chip with solder bumps. At this time, in Examples 1 to 7 and Comparative Example 1, the semiconductor chip with solder bumps was attached from the first adhesive layer side (the side opposite to the second adhesive layer). Next, the stack was mounted on a glass epoxy substrate (glass epoxy substrate: thickness 420 μm, copper wiring: thickness 9 μm) from the evaluation sample side using a flip mounting device "FCB3" (manufactured by Panasonic Corporation, product name). The mounting was performed under the conditions of a crimping head temperature of 350°C, a crimping time of 3 seconds, and a crimping pressure of 0.5 MPa. Thus, a connection structure (semiconductor device) in which a glass epoxy substrate and a semiconductor chip with solder bumps were daisy-chained was obtained.

[0261] (Rounded Corner Amount)

[0262] The connection structure obtained in the above was observed from the semiconductor chip side using a digital microscope VHX-6000 (manufactured by KEYENCE CORPORATION), and the length of the adhesive (rounded corners) overflowing from the four sides around the semiconductor chip was measured. As the length of the rounded corners of each side, the maximum value of the shortest distance from the end of the overflowing adhesive to the semiconductor chip was used. Regarding the amount of rounded corners, an evaluation was performed based on the average value of the lengths of the rounded corners measured on each of the four sides. If the average value is less than 100 μm, it is judged that the amount of rounded corners generated is sufficiently reduced, and if the above average value is greater than 100 μm, it is judged that the rounded corner suppression effect is insufficient.

[0263] (Gap)

[0264] The connection structure obtained in the above was photographed with an ultrasonic imaging diagnostic device (product name "Insight-300", manufactured by INSIGHT Inc.), and the image of the adhesive layer (a layer composed of a cured product of a film-like adhesive for semiconductors) on the chip was retrieved using a scanner GT-9300UF (manufactured by Epson Corp., product name). The image processing software Adobe Photoshop (registered trademark) was used to perform color correction and two-tone conversion, thereby identifying the void portion, and the proportion of the void portion was calculated using a histogram. The area of ​​the adhesive portion on the chip was set to 100%, the case where the void generation rate was 5% or less was set to "A", the case where it was more than 5% and less than 10% was set to "B", and the case where it was more than 10% was set to "C" for evaluation.

[0265] (Sealing)

[0266] The connection structure obtained in the above was observed from the semiconductor chip side using a semiconductor / FPD inspection microscope MX63 (manufactured by OLYMPUS CORPORATION), and the length of the unfilled portion at the four corners of the chip was measured. The length of the unfilled portion was the maximum value of the shortest distance from the four corners of the chip to the filled portion. Regarding the sealing performance, if the length of the unfilled portion was less than 500 μm, it was evaluated as "A", and if it was more than 500 μm, it was evaluated as "B".

[0267] [Table 3]

[0268]

[0269] Explanation of symbols

[0270] 1, 1a - film adhesive for semiconductor, 2, 2a - first adhesive region, 3, 3a - second adhesive region, 4 - substrate, 5 - connection portion (first connection portion), 9 - base, 10 - connection portion (first connection portion), 11 - semiconductor device, 15 - wiring (first connection portion and second connection portion), 20 - semiconductor chip, 25 - base, 30 - connection bump, 32 - bump (first connection portion and second connection portion), 40 - sealing portion, 100, 200, 500 - semiconductor device, A - semiconductor wafer, A' - semiconductor chip.

Claims

1. A film-like adhesive for semiconductor, comprising a first adhesive region not containing a flux compound and a second adhesive region containing a flux compound along a thickness direction, The first adhesive region comprises a first epoxy resin, a first imidazole curing agent and a (meth) acrylic compound, The second adhesive region includes a second epoxy resin, a second imidazole curing agent and the flux compound.

2. The film adhesive for semiconductor according to claim 1, wherein The first adhesive region does not contain a radical polymerization initiator.

3. The film adhesive for semiconductor according to claim 1, wherein At least one of the first epoxy resin and the second epoxy resin includes an epoxy resin that is liquid at 25°C.

4. The film adhesive for semiconductor according to claim 1, wherein At least one of the first epoxy resin and the second epoxy resin includes a trisphenol methane epoxy resin.

5. The film-like adhesive for semiconductor according to claim 1, wherein At least one of the first imidazole-based curing agent and the second imidazole-based curing agent has a triazine ring.

6. The film adhesive for semiconductor according to claim 1, wherein The ratio of the content of the first epoxy resin in the first adhesive region to the content of the (meth)acrylic compound is 3 to 11 in terms of mass ratio.

7. The film adhesive for semiconductor according to claim 1, wherein The (meth)acrylic compound includes a multifunctional (meth)acrylic compound having 2 to 8 (meth)acryloyl groups.

8. The film adhesive for semiconductor according to claim 1, wherein The flux compound comprises a polycarboxylic acid.

9. The film-like adhesive for semiconductor according to claim 1, wherein The thickness of the first adhesive region is 1 to 50 μm, The thickness of the second adhesive region is 0.5 to 2 times the thickness of the first adhesive region. 10 . The film-like adhesive for semiconductor according to claim 1 , which is non-conductive. 11 . The film-like adhesive for semiconductor according to claim 1 , which is used to bond a semiconductor chip and a substrate and seal a gap between the semiconductor chip and the substrate.

12. A method for producing a film-like adhesive for a semiconductor, the method being the method for producing a film-like adhesive for a semiconductor according to any one of claims 1 to 11, comprising the step of providing one of a first adhesive layer and a second adhesive layer on the other, The first adhesive layer is a layer including the first epoxy resin, the first imidazole curing agent, and the (meth)acrylic compound but not including a flux compound. The second adhesive layer is a layer including the second epoxy resin, the second imidazole-based curing agent, and the flux compound.

13. An adhesive tape comprising: The film adhesive for semiconductor according to any one of claims 1 to 11; and The back grinding tape is provided on the film-like adhesive for semiconductor and on the side opposite to the first adhesive region side when viewed from the second adhesive region.

14. A method for manufacturing a semiconductor device, comprising: A step of preparing a semiconductor chip with a film-like adhesive, the semiconductor chip with a film-like adhesive comprising: a semiconductor chip, and the film-like adhesive for semiconductor according to any one of claims 1 to 11, which is arranged on the semiconductor chip in such a manner that a surface of the first adhesive region on the side opposite to the second adhesive region faces the semiconductor chip side; and The semiconductor chip with the film adhesive is placed on a substrate from the film adhesive side and heated to electrically connect a connection portion of the semiconductor chip and a connection portion of the substrate and seal a gap between the semiconductor chip and the substrate.

15. A semiconductor device comprising: a semiconductor chip having a first connection portion; a substrate having a second connection portion electrically connected to the first connection portion; and a sealing portion that joins the semiconductor chip and the substrate and fills a gap between the semiconductor chip and the substrate. The sealing portion is a cured product of the film-like adhesive for a semiconductor according to any one of claims 1 to 11.

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