WO2018225800A1 - 半導体用フィルム状接着剤、半導体装置の製造方法及び半導体装置 - Google Patents
半導体用フィルム状接着剤、半導体装置の製造方法及び半導体装置 Download PDFInfo
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- WO2018225800A1 WO2018225800A1 PCT/JP2018/021767 JP2018021767W WO2018225800A1 WO 2018225800 A1 WO2018225800 A1 WO 2018225800A1 JP 2018021767 W JP2018021767 W JP 2018021767W WO 2018225800 A1 WO2018225800 A1 WO 2018225800A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16135—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
- H01L2224/16145—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
- H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
Definitions
- the present invention relates to a film adhesive for semiconductor, a method for manufacturing a semiconductor device, and a semiconductor device.
- a COB (Chip On Board) type connection method that is widely used in BGA (Ball Grid Array), CSP (Chip Size Package), and the like also corresponds to the FC connection method.
- the FC connection method is also widely used in a COC (Chip On Chip) type connection method in which connection portions (for example, bumps and wirings) are formed on a semiconductor chip to connect the semiconductor chips.
- chip stack type packages For packages that are strongly required to be further reduced in size, thickness and functionality, chip stack type packages, POP (Package On Package), TSV (Through, etc.), in which chips are stacked by using the connection method described above, are multi-staged. -Silicon Via) etc. are also starting to spread widely.
- Such stacking / multi-stage technology arranges semiconductor chips and the like three-dimensionally, so that the package can be made smaller than the two-dimensional arrangement technique.
- it is effective as a next-generation semiconductor wiring technology because it is effective for improving semiconductor performance, reducing noise, reducing mounting area, and saving power.
- connection reliability for example, insulation reliability
- the main metal used for the connection part include solder, tin, gold, silver, copper, nickel, and the like, and conductive materials including a plurality of these are also used.
- the metal used for the connection part may oxidize on the surface and produce an oxide film, and impurities such as oxide may adhere to the surface, which may cause impurities on the connection surface of the connection part. is there. If such impurities remain, connection reliability (for example, insulation reliability) between the semiconductor chip and the substrate or between the two semiconductor chips decreases, and the merit of employing the above-described connection method is impaired. There is concern.
- connection portion known by OSP (Organic Solderability Preservatives) processing with an anti-oxidation film
- OSP Organic Solderability Preservatives
- this anti-oxidation film has a solder wettability during the connection process. May cause a decrease in connectivity and connectivity.
- Patent Document 1 a method using a single layer film containing a flux agent in a semiconductor material (see, for example, Patent Document 1), a heat containing a thermosetting resin layer and an acid component.
- Patent Document 2 A method using a two-layer film composed of a plastic resin layer has been proposed (see, for example, Patent Document 2).
- an object of the present invention is to provide a film-like adhesive for semiconductors that can obtain excellent connection reliability even when the crimping time is shortened.
- Another object of the present invention is to provide a semiconductor device using such a semiconductor film adhesive and a method for manufacturing the same.
- the film-like adhesive for semiconductors of the present invention is provided on the first layer comprising the first thermosetting adhesive containing the flux compound and the first layer, and substantially contains no flux compound. And a second layer made of two thermosetting adhesives.
- the second layer is not easily affected by the flux compound, so that the second layer is cured quickly and sufficiently after the connecting portions are brought into contact with each other. Can be expressed.
- the film-like adhesive described in Patent Document 2 has a high possibility that the thermoplastic resin is softened at a high temperature such as pressure bonding, and troubles such as peeling occur, which is a problem from the viewpoint of reliability.
- the film-like adhesive for semiconductor of the present invention hardly causes such a problem. For these reasons, according to the film adhesive for semiconductor of the present invention, excellent connection reliability (for example, insulation reliability) can be obtained even when the pressure bonding is performed at a high temperature in a short time.
- the film-like adhesive for semiconductors of the present invention it is possible to shorten the pressure bonding time, so that productivity can be improved. Further, according to the film adhesive for semiconductor of the present invention, the flip chip package can be easily enhanced in function and integrated.
- a conventional semiconductor adhesive for example, a film-like adhesive described in Patent Document 1
- high-temperature pressure bonding is performed in a state where the semiconductor adhesive is not sufficiently cured, and voids are formed. May occur, and peeling may occur inside the package starting from voids.
- the peeling inside the package becomes large, stress is applied to the connecting portion and a crack is generated, so that the peeling inside the package leads to poor connection of the package.
- the film-like adhesive for semiconductor of the present invention since it can be sufficiently cured in a short time, generation of voids can be easily suppressed.
- the second layer substantially containing no flux compound is rapidly cured, so that even if microvoids are generated, the expansion of the voids is suppressed, and the visual recognition It is difficult to generate a void that is as large as possible.
- the adhesive When a flip chip package is manufactured using a conventional film adhesive, the adhesive may not protrude from the periphery of the chip because the adhesive is not cured in a short time. Such protrusion of the adhesive hinders the mounting of adjacent chips, leading to a reduction in the number of packages that can be mounted per wafer. That is, when the adhesive protrudes from the periphery of the chip, the productivity decreases. In addition, if the amount of protruding adhesive is excessive, the protruding adhesive may crawl onto the mounted chip, causing damage to the mounted chip when another chip is mounted on the chip. obtain. On the other hand, according to the film-like adhesive for semiconductor of the present invention, it is possible to sufficiently cure in a short time, and thus it is possible to prevent the adhesive from protruding.
- solder, copper, and the like tend to be used as the metal for the connection portion in place of gold that is not easily corroded for the purpose of cost reduction.
- OSP Organic Solderability Preservative
- the second thermosetting adhesive preferably has a curing reaction rate of 80% or more when held at 200 ° C. for 5 seconds. In this case, better connection reliability can be obtained even when the pressure bonding is performed at a high temperature in a short time.
- the second thermosetting adhesive preferably contains a radical polymerizable compound and a thermal radical generator.
- a radical polymerizable compound and a thermal radical generator.
- the thermal radical generator is preferably a peroxide. In this case, since the further excellent handling property and storage stability are obtained, the further excellent connection reliability is easy to be obtained.
- the radical polymerizable compound is preferably a (meth) acrylic compound. In this case, it is easy to obtain better connection reliability.
- the (meth) acrylic compound preferably has a fluorene skeleton. In this case, it is easy to obtain better connection reliability.
- the flux compound preferably has a carboxyl group, and more preferably has two or more carboxyl groups. In this case, it is easy to obtain better connection reliability.
- the flux compound is preferably a compound represented by the following formula (2).
- R 1 and R 2 each independently represent a hydrogen atom or an electron-donating group, and n represents 0 or an integer of 1 or more.
- the melting point of the flux compound is preferably 150 ° C. or lower.
- the flux is melted before the adhesive is cured at the time of thermocompression bonding, and the oxide film such as solder is reduced and removed, so that it is easy to obtain better connection reliability.
- the first thermosetting adhesive preferably contains a curing agent, and the curing agent is more preferably an imidazole curing agent. In this case, it is easy to obtain better connection reliability.
- a semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or each connection portion of a plurality of semiconductor chips is electrically connected to each other.
- a method for manufacturing a semiconductor device comprising the step of sealing at least a part of a connecting portion using the above-described film-like adhesive for semiconductor.
- a semiconductor device having excellent connection reliability for example, insulation reliability
- a semiconductor device excellent in connection reliability for example, insulation reliability
- the semiconductor device of the present invention is a semiconductor device in which the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other, or the semiconductor device in which the connection portions of the plurality of semiconductor chips are electrically connected to each other. And at least one part of the connection part is sealed with the hardened
- This semiconductor device is excellent in continuous reliability (for example, insulation reliability).
- the present invention it is possible to provide a film adhesive for a semiconductor that can obtain excellent connection reliability even when the crimping time is shortened. Moreover, according to this invention, the semiconductor device using such a film-form adhesive for semiconductors and its manufacturing method can be provided.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention.
- FIG. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
- FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
- FIG. 4 is a process cross-sectional view schematically showing one embodiment of a method for manufacturing a semiconductor device of the present invention.
- (meth) acrylate means at least one of acrylate and methacrylate corresponding thereto.
- the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the film-like adhesive for semiconductors of this embodiment is a first layer (flux-containing layer) composed of a first thermosetting adhesive containing a flux compound (hereinafter also simply referred to as “first adhesive”). ) And a second layer comprising a second thermosetting adhesive (hereinafter also simply referred to as “second adhesive”) provided on the first layer and containing substantially no flux compound. Flux-free layer).
- the film-like adhesive for semiconductor of this embodiment is, for example, a non-conductive adhesive (film-like non-conductive adhesive for semiconductor), and the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other.
- a connected semiconductor device or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other it is used for sealing at least a part of the connection portion.
- the crimping time (for example, the crimping time in the crimping process for joining the semiconductor chip and the printed circuit board) is shortened. Even if it is a case (for example, when crimping time is 5 seconds or less), excellent connection reliability can be obtained.
- the first adhesive contains, for example, a thermosetting component and a flux compound.
- the thermosetting component include a thermosetting resin and a curing agent.
- the thermosetting resin include an epoxy resin, a phenol resin (except when contained as a curing agent), a polyimide resin, and the like. Among these, it is preferable that the thermosetting resin is an epoxy resin.
- the film-form adhesive for semiconductors of this embodiment may contain the high molecular component and filler whose weight average molecular weight is 10,000 or more as needed.
- the first adhesive comprises an epoxy resin (hereinafter sometimes referred to as “component (a)”), a curing agent (hereinafter sometimes referred to as “component (b)”), and a flux compound (hereinafter referred to as “component (a)”).
- component (c) it is referred to as “component (c)”
- component (d) a polymer component having a weight average molecular weight of 10,000 or more
- component (E) component a filler
- (A) component epoxy resin
- Any epoxy resin can be used without particular limitation as long as it has two or more epoxy groups in the molecule.
- the component (a) 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, triphenyl A methane type epoxy resin, a dicyclopentadiene type epoxy resin, and various polyfunctional epoxy resins can be used. These can be used alone or as a mixture of two or more.
- the thermal weight loss rate at 250 ° C. is 5% or less. It is preferable to use an epoxy resin.
- the temperature at the time of connection is 300 ° C., it is preferable to use an epoxy resin having a thermal weight loss rate of 5% or less at 300 ° C.
- the content of the component (a) is, for example, 5 to 75% by mass, preferably 10 to 50% by mass, and more preferably 15 to 35% by mass based on the total mass of the first adhesive.
- component (b) curing agent
- component (b) examples include phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, and phosphine curing agents.
- component (B) When the component contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, it exhibits a flux activity that suppresses the formation of an oxide film at the connection part, and improves connection reliability and insulation reliability. it can.
- each curing agent will be described.
- Phenolic resin-based curing agent The phenolic resin-based curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule.
- phenol novolak resin, cresol novolac resin, phenol aralkyl resin Cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin and various polyfunctional phenol resins can be used. These can be used alone or as a mixture of two or more.
- Equivalent ratio of phenol resin-based curing agent to component (a) is excellent curability and adhesiveness. From the viewpoint of storage stability, 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. When the equivalence ratio is 0.3 or more, the curability tends to be improved and the adhesive force tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted phenolic hydroxyl group does not remain excessively, and the water absorption is increased. It tends to be kept low and the insulation reliability improves.
- Acid anhydride curing agent examples include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol bis.
- Anhydro trimellitate can be used. These can be used alone or as a mixture of two or more.
- the equivalent ratio of the acid anhydride curing agent to the component (a) is good curability. From the viewpoint of adhesiveness and storage stability, 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. When the equivalence ratio is 0.3 or more, the curability is improved and the adhesive force tends to be improved. When the equivalent ratio is 1.5 or less, the unreacted acid anhydride does not remain excessively, and the water absorption rate is increased. It tends to be kept low and the insulation reliability improves.
- Amine-based curing agent for example, dicyandiamide can be used.
- Equivalent ratio of amine-based curing agent to component (a) is good curability, adhesion and storage From the viewpoint of stability, 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is still more preferable. If the equivalence ratio is 0.3 or more, the curability tends to be improved and the adhesive strength tends to be improved. If the equivalent ratio is 1.5 or less, excessive unreacted amine does not remain and the insulation reliability is improved. Tend to.
- Imidazole-based curing agent examples include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2′-ethyl-4′-methylimidazolyl
- the content of the imidazole curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of component (a).
- component (a) There exists a tendency for sclerosis
- curing agent is 0.1 mass part or more.
- the content of the imidazole-based curing agent is 20 parts by mass or less, the fluidity of the first adhesive at the time of pressure bonding can be ensured, and the first adhesive between the connection parts is sufficiently eliminated. be able to. As a result, since the first adhesive is prevented from being cured while intervening between the solder and the connecting portion, poor connection is unlikely to occur.
- (V) Phosphine curing agent examples include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate. Be listed.
- the content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (a). If the content of the phosphine-based curing agent is 0.1 parts by mass or more, the curability tends to be improved, and if it is 10 parts by mass or less, the first adhesive is cured before the metal bond is formed. No connection failure is likely to occur.
- a phenol resin curing agent, an acid anhydride curing agent, and an amine curing agent can be used singly or as a mixture of two or more.
- the imidazole-based curing agent and the phosphine-based curing agent may each be used alone, but may be used together with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.
- the first adhesive contains a phenol resin curing agent, an acid anhydride curing agent, or an amine curing agent as the component (b), it exhibits a flux activity for removing the oxide film and further improves connection reliability. be able to.
- the component (c) is a compound having a flux activity, and functions as a flux agent in the first adhesive.
- any known component can be used without particular limitation as long as the oxide film on the surface of solder or the like is reduced and removed to facilitate metal bonding.
- one type of flux compound may be used alone, or two or more types of flux compounds may be used in combination.
- the curing agent which is the component (b) is not included in the component (c).
- the flux compound preferably has a carboxyl group, and more preferably has two or more carboxyl groups, from the viewpoint of obtaining sufficient flux activity and better connection reliability.
- a compound having two carboxyl groups is preferable. Compared with a compound having one carboxyl group (monocarboxylic acid), a compound having two carboxyl groups is less likely to volatilize even at a high temperature during connection, and the generation of voids can be further suppressed.
- the use of a compound having two carboxyl groups further suppresses the increase in viscosity of the film adhesive for semiconductors during storage and connection work compared to the case of using a compound having three or more carboxyl groups. Thus, the connection reliability of the semiconductor device can be further improved.
- the flux compound having a carboxyl group a compound having a group represented by the following formula (1) is preferably used.
- R 1 represents a hydrogen atom or an electron donating group.
- R 1 is preferably electron donating.
- the first adhesive contains an epoxy resin and a curing agent, and among the compounds having a group represented by the formula (1), R 1 is an electron donating group.
- the epoxy resin and the curing agent react with each other and the curing reaction proceeds.
- the carboxylic acid as the flux compound is taken into the curing reaction. That is, an ester bond may be formed by the reaction between the epoxy group of the epoxy resin and the carboxyl group of the flux compound. This ester bond is likely to cause hydrolysis due to moisture absorption or the like, and this decomposition of the ester bond is considered to be a cause of a decrease in adhesive strength after moisture absorption.
- the first adhesive is a compound having a group in which R 1 is an electron donating group, that is, an electron donating group in the vicinity.
- R 1 is an electron donating group
- the flux activity is sufficiently obtained by the carboxyl group, and even when the above ester bond is formed, the electron density of the ester bond portion is reduced by the electron donating group. The degradation of the rising ester bond is suppressed.
- a substituent electro-donating group exists in the vicinity of the carboxyl group, it is considered that the reaction between the carboxyl group and the epoxy resin is suppressed due to steric hindrance, and it is difficult to generate an ester bond.
- the first adhesive further containing a compound in which R 1 is an electron donating group when used, a composition change occurs due to moisture absorption or the like. Difficult to maintain excellent adhesion.
- the above-described action is such that the curing reaction between the epoxy resin and the curing agent is not easily inhibited by the flux compound, and due to this action, the connection reliability due to sufficient progress of the curing reaction between the epoxy resin and the curing agent. The effect of improvement can also be expected.
- the electron donating group When the electron donating property of the electron donating group becomes strong, the effect of suppressing the decomposition of the ester bond tends to be easily obtained. Moreover, when the steric hindrance of the electron donating group is large, an effect of suppressing the reaction between the carboxyl group and the epoxy resin is easily obtained.
- the electron donating group preferably has a good balance of electron donating properties and steric hindrance.
- the electron donating group examples include an alkyl group, a hydroxyl group, an amino group, an alkoxy group, and an alkylamino group.
- the electron donating group is preferably a group that does not easily react with other components (for example, the epoxy resin of component (a)). Specifically, an alkyl group, a hydroxyl group, or an alkoxy group is preferable, and an alkyl group is more preferable.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- the carbon number of the alkyl group increases, the electron donating property and steric hindrance tend to increase. Since the alkyl group having the carbon number in the above range is excellent in the balance between electron donating property and steric hindrance, the effect of the present invention is more remarkably exhibited by the alkyl group.
- the alkyl group may be linear or branched, and is preferably linear.
- the number of carbon atoms of the alkyl group is preferably not more than the number of carbon atoms in the main chain of the flux compound from the viewpoint of the balance between electron donating properties and steric hindrance.
- the flux compound is a compound represented by the following formula (2) and the electron donating group is a linear alkyl group
- the carbon number of the alkyl group is the carbon number of the main chain of the flux compound ( n + 1) or less.
- an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
- an alkoxy group having 1 to 5 carbon atoms is more preferable.
- An alkoxy group having a carbon number in the above range is excellent in the balance between electron donating property and steric hindrance, and therefore the effect of the present invention is more remarkably exhibited by the alkoxy group.
- the alkyl group portion of the alkoxy group may be linear or branched, and is preferably linear.
- the number of carbon atoms of the alkoxy group is preferably not more than the number of carbon atoms in the main chain of the flux compound from the viewpoint of the balance between electron donating properties and steric hindrance.
- the flux compound is a compound represented by the following formula (2) and the electron donating group is a linear alkoxy group
- the number of carbon atoms in the alkoxy group is the number of carbon atoms in the main chain of the flux compound ( n + 1) or less.
- alkylamino group examples include a monoalkylamino group and a dialkylamino group.
- a monoalkylamino group having 1 to 10 carbon atoms is preferable, and a monoalkylamino group having 1 to 5 carbon atoms is more preferable.
- the alkyl group portion of the monoalkylamino group may be linear or branched, and is preferably linear.
- dialkylamino group a dialkylamino group having 2 to 20 carbon atoms is preferable, and a dialkylamino group having 2 to 10 carbon atoms is more preferable.
- the alkyl group portion of the dialkylamino group may be linear or branched, and is preferably linear.
- a compound represented by the following formula (2) can be suitably used. According to the compound represented by the following formula (2), the reflow resistance and connection reliability of the semiconductor device can be further improved.
- R 1 and R 2 each independently represent a hydrogen atom or an electron donating group, and n represents 0 or an integer of 1 or more.
- a plurality of R 2 may be the same or different.
- R 1 has the same meaning as R 1 in Formula (1). Further, the electron donating property represented by R 2 is the same as the above-described example of the electron donating group described as R 1 . For the same reason as described in the formula (1), R 1 in the formula (2) is preferably an electron donating group.
- N in Formula (2) is preferably 1 or more.
- n in the formula (2) is preferably 15 or less, more preferably 11 or less, and may be 6 or less or 4 or less. When n is 15 or less, further excellent connection reliability can be obtained.
- a compound represented by the following formula (3) is more preferable. According to the compound represented by the following formula (3), the reflow resistance and connection reliability of the semiconductor device can be further improved.
- R 1 and R 2 each independently represent a hydrogen atom or an electron donating group, and m represents 0 or an integer of 1 or more.
- R 1 and R 2 have the same meanings as R 1 and R 2 in Formula (2).
- M in Formula (3) is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. When m is 10 or less, further excellent connection reliability can be obtained.
- R 1 and R 2 may be a hydrogen atom or an electron donating group. From the viewpoint of obtaining better connection reliability, it is preferable that at least one of R 1 and R 2 is an electron donating group. If R 1 is an electron donating group and R 2 is a hydrogen atom, the melting point tends to be low, and the connection reliability of the semiconductor device may be further improved. Further, if R 1 and R 2 are different electron donating groups, the melting point tends to be lower than that in the case where R 1 and R 2 are the same electron donating group. In some cases, reliability can be further improved.
- Examples of the flux compound include dicarboxylic acids selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, and 2 of these dicarboxylic acids.
- a compound in which an electron donating group is substituted at the position can be used.
- the melting point of the flux compound is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. Such a flux compound is likely to exhibit sufficient flux activity before the curing reaction between the epoxy resin and the curing agent occurs. Therefore, according to the film adhesive for a semiconductor using the first adhesive containing such a flux compound, it is possible to realize a semiconductor device that is further excellent in connection reliability. Further, the melting point of the flux compound is preferably 25 ° C. or higher, and more preferably 50 ° C. or higher. The flux compound is preferably solid at room temperature (25 ° C.).
- the melting point of the flux compound can be measured using a general melting point measuring apparatus.
- the sample for measuring the melting point is required to reduce the temperature deviation in the sample by being pulverized into fine powder and using a small amount.
- a capillary tube with one end closed is often used.
- some measuring apparatuses are sandwiched between two microscope cover glasses to form a container. If the temperature is rapidly increased, a temperature gradient is generated between the sample and the thermometer, resulting in a measurement error. Therefore, the heating at the time of measuring the melting point can be measured at an increase rate of 1 ° C. or less per minute. desirable.
- the sample for measuring the melting point is prepared as a fine powder as described above, the sample before melting is opaque due to irregular reflection on the surface. Usually, the temperature at which the appearance of the sample begins to become transparent is taken as the lower limit of the melting point, and the temperature at which the sample has completely melted is taken as the upper limit.
- the most classic device is a device in which a capillary tube packed with a sample is attached to a double tube thermometer and heated in a warm bath.
- a highly viscous liquid is used as the liquid in the warm bath, and concentrated sulfuric acid or silicon oil is often used, so that the sample comes near the reservoir at the tip of the thermometer. Install.
- the melting point measuring device it is possible to use a device that uses a metal heat block for heating and automatically determines the melting point while adjusting the heating while measuring the light transmittance.
- the melting point of 150 ° C. or lower means that the upper limit of the melting point is 150 ° C. or lower, and the melting point of 25 ° C. or higher means that the lower limit of the melting point is 25 ° C. or higher. means.
- the content of the component (c) is preferably 0.5 to 10% by mass and more preferably 0.5 to 5% by mass based on the total mass of the first adhesive.
- the 1st adhesive agent may contain the high molecular component ((d) component) whose weight average molecular weight is 10,000 or more as needed.
- the first adhesive containing the component (d) is further excellent in heat resistance and film formability.
- the component (d) examples include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane. Resin and acrylic rubber are mentioned. Among these, phenoxy resin, polyimide resin, urethane resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin are preferable, and phenoxy resin, polyimide resin, urethane resin, and acrylic rubber are more preferable from the viewpoint of excellent heat resistance and film formability. Phenoxy resin, urethane resin and acrylic rubber are particularly preferable. These components (d) can be used alone or as a mixture or copolymer of two or more. However, the component (d) does not include a compound corresponding to the component (a) and a compound corresponding to the component (e).
- the weight average molecular weight of the component (d) is, for example, 10,000 or more, preferably 20000 or more, and more preferably 30000 or more. According to such a component (d), the heat resistance and film formability of the first adhesive can be further improved.
- the weight average molecular weight of the component (d) is preferably 200000 or less, and more preferably 100000 or less. According to such a component (d), the heat resistance of the first adhesive can be further improved. From these viewpoints, the weight average molecular weight of the component (d) may be 10,000 to 200,000, 20,000 to 100,000, or 30,000 to 100,000.
- the weight average molecular weight means a weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (manufactured by Shimadzu Corporation, trade name: C-R4A).
- C-R4A high performance liquid chromatography
- the ratio C a / C d (mass ratio) of the content C a of the component (a) to the content C d of the component (d) is 0.01. Is preferably 5 to 5, more preferably 0.05 to 3, and still more preferably 0.1 to 2.
- the first adhesive may contain a filler (component (e)) as necessary.
- a filler component (e)
- the viscosity of the first adhesive, the physical properties of the cured product of the first adhesive, and the like can be controlled.
- the component (e) for example, it is possible to suppress the generation of voids at the time of connection and to reduce the moisture absorption rate of the cured product of the first adhesive.
- an inorganic filler inorganic particle
- an organic filler organic particle
- the inorganic filler include insulating inorganic fillers such as glass, silica, alumina, titanium oxide, mica, and boron nitride. Among them, at least one selected from the group consisting of silica, alumina, titanium oxide, and boron nitride is included. Preferably, at least one selected from the group consisting of silica, alumina, and boron nitride is more preferable.
- the insulating inorganic filler may be a whisker.
- whiskers examples include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, and boron nitride.
- a resin filler resin particle
- the resin filler include polyurethane and polyimide.
- the resin filler can give flexibility at a high temperature such as 260 ° C. as compared with the inorganic filler, so that it is suitable for improving reflow resistance and can be given flexibility, so that it can improve film formability. effective.
- the content of the inorganic filler makes it easy to adjust the elastic modulus within a desired range, and can suppress the generation of voids while suppressing warpage, and further provides excellent connection reliability. From the viewpoint, it may be 50% by mass or more, 70% by mass or more, or 80% by mass or more based on the total mass of the component (e). The content of the inorganic filler may be 100% by mass or less or 90% by mass or less.
- the component (e) is preferably insulating (insulating filler). It is preferable that the first adhesive does not contain a conductive metal filler (metal particles) such as a silver filler and a solder filler, and a conductive inorganic filler such as carbon black.
- a conductive metal filler metal particles
- a conductive inorganic filler such as carbon black.
- the content of the insulating filler makes it easy to adjust the elastic modulus to a desired range, and can suppress the generation of voids while suppressing warpage, and further provides excellent connection reliability. In view of the above, it may be 50% by mass or more, 70% by mass or more, or 90% by mass or more based on the total mass of the component (e).
- the component (e) may consist essentially of an insulating filler. That is, the component (e) may not substantially contain a conductive filler. “Not substantially contained” means that the content of the conductive filler in the component (e) is less than 0.5% by mass based on the total mass of the component (e).
- the physical properties of the component may be appropriately adjusted by surface treatment.
- the component (e) is preferably a surface-treated filler from the viewpoint of improving dispersibility or adhesive strength.
- the surface treatment agent include glycidyl (epoxy), amine, phenyl, phenylamino, (meth) acrylic, and vinyl compounds.
- a silane treatment with a silane compound such as an epoxy silane, amino silane, or acrylic silane is preferable because of easy surface treatment.
- the surface treating agent is preferably at least one selected from the group consisting of a glycidyl compound, a phenylamino compound, and a (meth) acrylic compound from the viewpoint of excellent dispersibility, fluidity, and adhesive strength.
- the surface treatment agent is preferably at least one selected from the group consisting of phenyl compounds and (meth) acrylic compounds from the viewpoint of excellent storage stability.
- the average particle size of the component (e) is preferably 1.5 ⁇ m or less from the viewpoint of preventing biting during flip chip connection, and more preferably 1.0 ⁇ m or less from the viewpoint of excellent visibility (transparency).
- the content of the component (e) is based on the total mass of the first adhesive from the viewpoint of suppressing a decrease in heat dissipation, and from the viewpoint of easily suppressing the generation of voids, an increase in moisture absorption, and the like. As a standard, 15 mass% or more is preferable, 20 mass% or more is more preferable, and 40 mass% or more is still more preferable.
- the content of the component (e) is easily suppressed from increasing the viscosity and reducing the fluidity of the first adhesive and causing the filler to bite into the connecting portion (trapping). From the viewpoint of easily suppressing the deterioration of the properties, 90% by mass or less is preferable and 80% by mass or less is more preferable based on the total mass of the first adhesive. From these viewpoints, the content of the component (e) is preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 40 to 80% by mass based on the total mass of the first adhesive. preferable.
- blend additives such as antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trap agent, with a 1st adhesive agent.
- additives such as antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trap agent, with a 1st adhesive agent.
- the minimum melt viscosity of the first adhesive is preferably 1000 Pa ⁇ s or more, more preferably 1500 Pa ⁇ s or more, and further preferably 2000 Pa ⁇ s or more.
- the minimum melt viscosity is 1000 Pa ⁇ s or more, it is possible to suppress the thermal expansion of the voids involved during mounting, and the possibility of peeling during long-term use (for example, a reliability test) is reduced.
- the first layer is sufficiently eliminated at the time of solder connection, and the resin bite is reduced, the electrical connection reliability is excellent.
- the minimum melt viscosity of the first adhesive is preferably 10,000 Pa ⁇ s or less, 5000 Pa ⁇ s or less is more preferable, and 4000 Pa ⁇ s or less is still more preferable. From these viewpoints, the minimum melt viscosity of the first adhesive is preferably 1000 to 10,000 Pa ⁇ s, more preferably 1500 to 5000 Pa ⁇ s, and still more preferably 2000 to 4000 Pa ⁇ s.
- the melt viscosity can be measured using a rotary rheometer (for example, ARES-G2 manufactured by TA Instruments).
- the said melt viscosity is a melt viscosity measured on condition of the following. Measurement conditions Temperature rising rate: 10 ° C./min Frequency: 10 Hz Temperature range: 30-150 ° C
- the second adhesive does not substantially contain a flux compound. “Substantially not containing” means that the content of the flux compound in the second adhesive is less than 0.5 mass% based on the total mass of the second adhesive.
- the second adhesive preferably has a curing reaction rate of 80% or more when held at 200 ° C. for 5 seconds from the viewpoint that the effects of the present invention are remarkably obtained.
- Examples of such a second adhesive include radical curing adhesives. The reason why the effect of the present invention is remarkably obtained by such an adhesive is not clear, but the present inventors presume as follows.
- the flux component deactivates radicals, and thus a radical curing system cannot be applied, and a cationic curing system using epoxy or the like is applied.
- this curing system reaction system
- curing proceeds by a nucleophilic addition reaction, so the curing rate is slow, and voids may occur after pressure bonding.
- defects for example, peeling of the semiconductor material at a reflow temperature of around 260 ° C., poor connection at the connection portion, etc.
- the curing system can be a radical curing system, and a sufficient curing rate can be obtained. Therefore, it is presumed that by using the above-mentioned second adhesive for the second layer, voids are hardly generated even when the pressure bonding is performed at a high temperature and in a short time, and the effect of the present invention becomes remarkable.
- a sufficient curing speed can be obtained, for example, even when solder is used for the connection portion, the film adhesive is cured in a temperature region lower than the solder melting temperature. Can be made. Therefore, it is possible to sufficiently suppress the occurrence of poor connection due to solder scattering and flow.
- the second adhesive is necessary to be a radical polymerizable compound (hereinafter sometimes referred to as “component (A)”) and a thermal radical generator (hereinafter sometimes referred to as “component (B)”). Accordingly, an embodiment containing a polymer component (hereinafter sometimes referred to as “component (C)”) and a filler (hereinafter sometimes referred to as “component (D)”) will be described.
- component (A) a radical polymerizable compound
- component (B) thermal radical generator
- component (C) polymer component
- component (D) filler
- the component (A) is a compound that can undergo a radical polymerization reaction with generation of radicals by heat, light, radiation, electrochemical action, or the like.
- Examples of the component (A) include (meth) acrylic compounds and vinyl compounds.
- a (meth) acrylic compound is preferable from the viewpoint of excellent durability, electrical insulation, and heat resistance.
- the (meth) acrylic compound is not particularly limited as long as it is a compound having one or more (meth) acrylic groups ((meth) acryloyl groups) in the molecule.
- bisphenol A type bisphenol F type, naphthalene type, (Meth) acrylic compounds containing a skeleton of phenol novolac type, cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type, adamantane type or isocyanuric acid type; ) Acrylic compounds (excluding (meth) acrylic compounds containing the skeleton) can be used.
- polyfunctional (meth) acrylic compound examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and trimethylolpropane di (meth) acrylate.
- a component can be used individually by 1 type or in combination of 2 or more types.
- the component (A) has a bisphenol A skeleton, a bisphenol F skeleton, a naphthalene skeleton, a fluorene skeleton, an adamantane skeleton or an isocyanuric acid skeleton from the viewpoint of excellent heat resistance and the suppression of voids. It is more preferable that it has a fluorene type skeleton. From the viewpoint of further suppressing the generation of voids, the component (A) is more preferably a (meth) acrylate having any of the skeletons described above.
- the component (A) is preferably solid at room temperature (25 ° C.).
- the solid is less likely to generate voids than the liquid, and the viscosity (tack) of the second adhesive before curing (B stage) is small and excellent in handleability.
- Examples of the component (A) that is solid at room temperature (25 ° C.) include (meth) acrylates having a bisphenol A skeleton, a fluorene skeleton, an adamantane skeleton, or an isocyanuric acid skeleton.
- the number of functional groups of the (meth) acryl group in the component (A) is preferably 3 or less.
- the number of functional groups is large, the curing network proceeds rapidly, and unreacted groups may remain.
- the number of functional groups is 3 or less, the number of functional groups does not increase excessively, and curing in a short time is likely to proceed sufficiently, so that it is easy to suppress a decrease in the curing reaction rate.
- the molecular weight of the component (A) is preferably smaller than 2000, and more preferably 1000 or less. The smaller the molecular weight of the component (A), the easier the reaction proceeds and the higher the curing reaction rate.
- the content of the component (A) is 10 mass% or more based on the total mass of the second adhesive from the viewpoint that the curing component is suppressed and the flow of the resin after curing is easily controlled. Is preferable, and 15 mass% or more is more preferable.
- the content of the component (A) is 50% by mass or less based on the total mass of the second adhesive from the viewpoint that the cured product is suppressed from becoming too hard and the package warpage is easily suppressed from increasing. Is preferable, and 40 mass% or less is more preferable. From these viewpoints, the content of the component (A) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass based on the total mass of the second adhesive.
- the content of the component (A) is 0.01 parts by mass or more with respect to 1 part by mass of the component (C) from the viewpoint that curability is suppressed from being lowered and adhesive strength is easily suppressed from being reduced.
- 0.05 mass part or more is more preferable, and 0.1 mass part or more is still more preferable.
- the content of the component (A) is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 1 part by mass of the component (C), from the viewpoint that the film formability is likely to be suppressed. From these viewpoints, the content of the component (A) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 1 part by weight of the component (C). 5 parts by mass is more preferable.
- the component (B) is not particularly limited as long as it functions as a curing agent for the component (A), but a thermal radical generator is preferable from the viewpoint of excellent handleability.
- thermal radical generator examples include azo compounds and peroxides (organic peroxides etc.).
- a peroxide is preferable, and an organic peroxide is more preferable.
- the radical reaction does not proceed in the step of drying the solvent in the film form, and the handleability and storage stability are excellent. Therefore, when using a peroxide as a thermal radical generator, it is easy to obtain better connection reliability.
- the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester.
- the organic peroxide is preferably at least one selected from the group consisting of hydroperoxide, dialkyl peroxide and peroxyester from the viewpoint of excellent storage stability. Further, the organic peroxide is preferably at least one selected from the group consisting of hydroperoxide and dialkyl peroxide from the viewpoint of excellent heat resistance. Examples of the dialkyl peroxide include dicumyl peroxide and di-tert-butyl peroxide.
- the content of the component (B) is preferably 0.5 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the component (A), from the viewpoint that curing proceeds sufficiently.
- the content of the component (B) is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the component (A).
- the content of the component (B) is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component (A).
- the second adhesive can further contain a polymer component.
- Component (C) is epoxy resin, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, (meth) acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal Resin, urethane resin, acrylic rubber, etc. are mentioned. Among them, epoxy resin, phenoxy resin, polyimide resin, (meth) acrylic resin, urethane resin, acrylic rubber, cyanate ester resin from the viewpoint of excellent heat resistance and film formability.
- (C) component can also be used as 1 type individually or 2 or more types of mixtures or copolymers. However, the component (C) does not include a compound corresponding to the component (A) and a compound corresponding to the component (D).
- the glass transition temperature (Tg) of the component (C) is preferably 120 ° C. or less, more preferably 100 ° C. or less, and even more preferably 85 ° C. or less, from the viewpoint of excellent stickability of the film adhesive for semiconductor to a substrate or chip. preferable.
- Tg glass transition temperature
- the thickness is within these ranges, bumps formed on the semiconductor chip, electrodes and wiring patterns formed on the substrate or wiring patterns can be easily embedded with a semiconductor film adhesive (a curing reaction starts). It is easy to suppress the occurrence of voids due to the remaining bubbles.
- Tg is measured using DSC (manufactured by Perkin Elmer Japan Co., Ltd., trade name: DSC-7 type) under the conditions of a sample amount of 10 mg, a heating rate of 10 ° C./min, and a measurement atmosphere: air.
- DSC manufactured by Perkin Elmer Japan Co., Ltd., trade name: DSC-7 type
- the weight average molecular weight of the component (C) is preferably 10,000 or more in terms of polystyrene, more preferably 30000 or more, even more preferably 40000 or more, and particularly preferably 50000 or more in order to exhibit good film-formability independently.
- a weight average molecular weight is 10,000 or more, it is easy to suppress that film forming property falls.
- the second adhesive is used to control the viscosity or the physical properties of the cured product, and to further suppress the generation of voids or the moisture absorption rate when the semiconductor chip and the substrate or the semiconductor chips are connected to each other. Furthermore, you may contain.
- (D) As a component the filler similar to the filler quoted as (e) component in a 1st adhesive agent can be used. The example of a preferable filler is also the same.
- the content of the component (D) is the total mass of the second adhesive from the viewpoint of suppressing the heat dissipation from decreasing and from the viewpoint of easily suppressing the generation of voids, the increase in moisture absorption, and the like. As a standard, 15 mass% or more is preferable, 20 mass% or more is more preferable, and 40 mass% or more is still more preferable.
- the content of the component (D) is easily suppressed from increasing the viscosity and reducing the fluidity of the second adhesive and causing the filler to be trapped (trapping). 90% by mass or less is preferable and 80% by mass or less is more preferable on the basis of the total mass of the second adhesive from the viewpoint of easily suppressing the deterioration of the properties. From these viewpoints, the content of the component (D) is preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 40 to 80% by mass based on the total mass of the second adhesive. preferable.
- the minimum melt viscosity of the second adhesive is not particularly limited, and may be a value higher than the minimum melt viscosity of the first adhesive, or may be a value lower than the minimum melt viscosity of the first adhesive. Good.
- the minimum melt viscosity of the second adhesive may be within a preferable range (for example, 1000 to 10000 Pa ⁇ s) of the minimum melt viscosity of the first adhesive described above.
- the minimum melt viscosity of the second adhesive can be measured by the same method as the minimum melt viscosity of the first adhesive.
- the curing reaction rate when the second adhesive is held at 200 ° C. for 5 seconds is preferably 80% or more, and more preferably 90% or more. If the curing reaction rate at 200 ° C. (solder melting temperature or lower) / 5 seconds is 80% or higher, it is easy to suppress the solder from scattering and flowing during connection (solder melting temperature or higher) and lowering the connection reliability.
- the curing reaction rate was calculated by adding 10 mg of the second adhesive (uncured flux-free layer) into an aluminum pan and then using DSC (trade name: DSC-7, manufactured by Perkin Elmer Japan Co., Ltd.) Can be obtained by measuring.
- Curing reaction rate (%) (1 ⁇ [calorific value of measurement sample after heat treatment] / [calorific value of untreated measurement sample]) ⁇ 100
- the second adhesive contains an anionically polymerizable epoxy resin (particularly an epoxy resin having a weight average molecular weight of 10,000 or more), it may be difficult to adjust the curing reaction rate to 80% or more. It is preferable that content of an epoxy resin is 20 mass parts or less with respect to 80 mass parts of (A) component, and it is more preferable that the epoxy resin is not contained.
- the second layer (flux-free layer) made of the second adhesive can be pressure-bonded at a high temperature of 200 ° C. or higher. Further, a flip chip package in which a metal such as solder is melted to form a connection exhibits further excellent curability.
- the thickness of the film-like adhesive for semiconductors of this embodiment when the sum of the heights of the connecting portions is x and the total thickness of the film-like adhesive for semiconductors is y, the relationship between x and y is From the viewpoints of connectivity during pressure bonding and adhesive filling properties, 0.70x ⁇ y ⁇ 1.3x is preferably satisfied, and 0.80x ⁇ y ⁇ 1.2x is more preferable.
- the total thickness of the film-like adhesive for semiconductor is, for example, 10 to 100 ⁇ m, 10 to 80 ⁇ m, or 10 to 50 ⁇ m.
- the thickness of the first layer may be, for example, 1 to 50 ⁇ m, 3 to 50 ⁇ m, 4 to 30 ⁇ m, or 5 to 20 ⁇ m.
- the thickness of the second layer may be, for example, 7 to 50 ⁇ m, 8 to 45 ⁇ m, or 10 to 40 ⁇ m.
- the ratio of the thickness of the second layer to the thickness of the first layer may be, for example, 0.1 to 10.0, It may be 0.5 to 6.0 and may be 1.0 to 4.0.
- the film adhesive for semiconductors of this embodiment may further include a layer other than the first layer and the second layer.
- the semiconductor film adhesive of this embodiment may include a mixed layer composed of a first layer and a second layer.
- the film-like adhesive for a semiconductor of the present embodiment is on the surface of the first layer opposite to the second layer and / or the surface of the second layer opposite to the first layer.
- a base film and / or a protective film may be provided thereon.
- an adhesive layer may be provided between the base film or the protective film and the first layer and / or between the base film or the protective film and the second layer.
- the first layer and the second layer may be adjacent to each other. In this case, it is preferable that the first layer and the second layer are formed so as not to be separated from each other.
- the peel strength between the first layer and the second layer may be 10 N / m or more.
- the minimum melt viscosity of the film adhesive is preferably 1000 Pa ⁇ s or more, more preferably 1500 Pa ⁇ s or more, and further preferably 2000 Pa ⁇ s or more.
- the minimum melt viscosity is 1000 Pa ⁇ s or more, it is possible to suppress the thermal expansion of the voids involved during mounting, and the possibility of peeling during long-term use (for example, a reliability test) is reduced.
- the first layer is sufficiently eliminated at the time of soldering and the resin bite is reduced, the electrical connection reliability is excellent. Therefore, the minimum melt viscosity of the film adhesive is preferably 10,000 Pa ⁇ s or less, and preferably 5000 Pa.
- the minimum melt viscosity of the film adhesive is preferably 1000 to 10,000 Pa ⁇ s, more preferably 1500 to 5000 Pa ⁇ s, and still more preferably 2000 to 4000 Pa ⁇ s.
- the minimum melt viscosity of the film adhesive can be measured by the same method as the minimum melt viscosity of the first adhesive.
- the film adhesive for semiconductors of this embodiment prepares the 1st film adhesive provided with the 1st layer, and the 2nd film adhesive provided with the 2nd layer, for example. It can be obtained by laminating a first film adhesive having a layer and a second film adhesive having a second layer.
- first film adhesive for example, first, (a) component, (b) component and (c) component, and (d) component and (e) component added as necessary
- the other components are added to an organic solvent and dissolved or dispersed by stirring, mixing, kneading or the like to prepare a resin varnish (coating varnish).
- the organic solvent is reduced by heating to form the base film or protective film.
- a first layer of the first adhesive can be formed thereon.
- organic solvent used for preparing the resin varnish those having characteristics capable of uniformly dissolving or dispersing each component are preferable.
- dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether examples include toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate.
- These organic solvents can be used alone or in combination of two or more.
- the stirring and mixing and kneading in preparing the resin varnish can be performed using, for example, a stirrer, a raking machine, a three roll, a ball mill, a bead mill or a homodisper.
- the base film and the protective film are not particularly limited as long as they have heat resistance that can withstand the heating conditions when volatilizing the organic solvent, polypropylene films, polyolefin films such as polymethylpentene films, polyethylene terephthalate films, Examples thereof include polyester films such as polyethylene naphthalate film, polyimide films, and polyetherimide films.
- a base film and a protective film are not restricted to the single-layer thing which consists of these films, The multilayer film which consists of 2 or more types of materials may be sufficient.
- said base film and protective film may be equipped with the adhesion layer on the one surface.
- the drying conditions when the organic solvent is volatilized from the resin varnish applied to the base film is preferably set so that the organic solvent is sufficiently volatilized, specifically, 50 to 200 ° C. for 0.1 to 90 minutes. It is preferable to perform heating. If there is no influence on the void or viscosity adjustment after mounting, the organic solvent is preferably removed to 1.5% by mass or less based on the total mass of the first film adhesive.
- the first layer is used except that other components such as the (A) component and the (B) component and the (C) component added as necessary are used.
- the 2nd layer which consists of a 2nd adhesive agent can be formed on a base film or a protective film by the method similar to.
- Examples of the method of bonding the first film adhesive and the second film adhesive include methods such as a heat press, roll lamination, and vacuum lamination. Lamination may be performed under heating conditions of 30 to 120 ° C., for example.
- the film-like adhesive for semiconductor of the present embodiment forms one of the first layer and the second layer on the base film, and then, on the obtained first layer or second layer, It may be obtained by forming the other of the first layer or the second layer.
- the film adhesive for semiconductors of this embodiment may be obtained, for example, by forming the first layer and the second layer substantially simultaneously on the base film.
- the first adhesive and the second adhesive are applied substantially simultaneously, and the first layer and the second layer are formed by drying at the same time (simultaneous multilayer coating method).
- a method of forming the first layer and the second layer by applying the second adhesive after applying the first adhesive and drying at once (sequential multilayer coating) Method).
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention.
- a semiconductor device 100 includes a semiconductor chip 10 and a substrate (circuit wiring board) 20 that face each other, and wirings 15 that are respectively disposed on mutually facing surfaces of the semiconductor chip 10 and the substrate 20.
- the semiconductor chip 10 and the substrate 20 are flip-chip connected by wiring 15 and connection bumps 30.
- the wiring 15 and the connection bump 30 are sealed with a hardened material of an adhesive and are shielded 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.
- the semiconductor device 200 includes a semiconductor chip 10 and a substrate 20 that face each other, a bump 32 that is disposed on a surface that faces the semiconductor chip 10 and the substrate 20, respectively, And a sealing portion 40 made of a cured product of an adhesive (first adhesive and second adhesive) filled in the gap between the substrates 20 without a gap.
- the semiconductor chip 10 and the substrate 20 are flip-chip connected by connecting opposing bumps 32 to each other.
- the bumps 32 are sealed with a hardened material of an adhesive and are shielded 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.
- FIG. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
- the semiconductor device 300 is the same as the semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wirings 15 and connection bumps 30.
- the semiconductor device 400 is the same as the semiconductor device 200 except that the two semiconductor chips 10 are flip-chip connected by the bumps 32.
- the semiconductor chip 10 is not particularly limited, and an elemental semiconductor composed of the same kind of element such as silicon or germanium, or a compound semiconductor such as gallium arsenide or indium phosphide can be used.
- the substrate 20 is not particularly limited as long as it is a circuit board, and an unnecessary portion of a metal film is etched on the surface of an insulating substrate mainly composed of glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, or the like.
- connection parts such as the wiring 15 and the bumps 32 have as main components gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.) ), Nickel, tin, lead, etc., and may contain a plurality of metals.
- gold, silver, and copper are preferable, and silver and copper are more preferable from the viewpoint of providing a package with excellent electrical and thermal conductivity of the connection portion.
- silver, copper, and solder which are inexpensive materials, are preferable, copper and solder are more preferable, and solder is more preferable.
- solder is more preferable.
- gold, silver, copper and solder are preferable, and gold, silver Solder is more preferable, and gold and silver are more preferable.
- the surface of the wiring 15 and the bump 32 is mainly made of gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc.
- the metal layer as a component may be formed by plating, for example. This metal layer may be composed of only a single component or may be composed of a plurality of components.
- the metal layer may have a structure in which a single layer or a plurality of metal layers are stacked.
- the semiconductor device of this embodiment may be formed by stacking a plurality of structures (packages) as shown in the semiconductor devices 100 to 400.
- the semiconductor devices 100 to 400 include gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel. May be electrically connected to each other through bumps, wirings, and the like.
- FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, which is a semiconductor device using the TSV technology.
- the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bumps 30, so that the semiconductor chip 10 and the interposer 50 are flip-chip connected.
- the gap between the semiconductor chip 10 and the interposer 50 is filled with a cured product of an adhesive (first adhesive and second adhesive) without any gaps, and constitutes the sealing portion 40.
- the semiconductor chip 10 On the surface of the semiconductor chip 10 opposite to the interposer 50, the semiconductor chip 10 is repeatedly stacked via the wiring 15, the connection bumps 30, and the sealing portion 40.
- the wirings 15 on the pattern surface on the front and back sides of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes that penetrate the inside of the semiconductor chip 10.
- the penetration electrode 34 copper, aluminum, etc. can be used as a material of the penetration electrode 34.
- Such a TSV technology makes it possible to acquire a signal from the back surface of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 passes vertically through the semiconductor chip 10, the distance between the semiconductor chips 10 facing each other and between the semiconductor chip 10 and the interposer 50 can be shortened and flexible connection is possible.
- the film adhesive for semiconductor of this embodiment can be applied as a film adhesive for semiconductor between the semiconductor chips 10 facing each other and between the semiconductor chip 10 and the interposer 50 in such a TSV technology.
- a semiconductor chip can be directly mounted on a motherboard without using an interposer.
- the film adhesive for semiconductor of this embodiment can also be applied when such a semiconductor chip is directly mounted on a mother board.
- the film adhesive for semiconductors of this embodiment can be applied also when sealing the space
- FIG. 4 is a diagram schematically showing one embodiment of a method for manufacturing a semiconductor device of the present invention.
- FIGS. 4A, 4B, and 4C showing the respective steps are semiconductor devices. The cross section of is shown.
- solder resist 60 having openings at positions where connection bumps 30 are formed is formed on a substrate 20 having wirings 15.
- the solder resist 60 is not necessarily provided. However, by providing a solder resist on the substrate 20, it is possible to suppress the occurrence of a bridge between the wirings 15 and improve the connection reliability and insulation reliability.
- the solder resist 60 can be formed using, for example, commercially available solder resist ink for packages. Specific examples of commercially available solder resist ink for packaging include SR series (trade name, manufactured by Hitachi Chemical Co., Ltd.) and PSR4000-AUS series (trade name, manufactured by Taiyo Ink Manufacturing Co., Ltd.).
- connection bumps 30 are formed in the openings of the solder resist 60.
- the surface on the second layer 41b side including the second adhesive is on the substrate 20 side on the substrate 20 on which the connection bumps 30 and the solder resist 60 are formed.
- a film-like adhesive for semiconductors of the present embodiment (hereinafter sometimes referred to as “film-like adhesive”) 41 is affixed.
- the film adhesive 41 can be attached by a hot press, roll lamination, vacuum lamination, or the like.
- the supply area and thickness of the film adhesive 41 are appropriately set depending on the size of the semiconductor chip 10 and the substrate 20, the height of the connection bump 30, and the like. Note that the film adhesive 41 may be attached so that the surface on the first layer 41a side including the first adhesive is on the substrate 20 side.
- the wiring 15 and the connection bumps 30 of the semiconductor chip 10 are aligned using a connection device such as a flip chip bonder. Subsequently, the semiconductor chip 10 and the substrate 20 are pressure-bonded while being heated at a temperature equal to or higher than the melting point of the connection bump 30 to connect the semiconductor chip 10 and the substrate 20 as shown in FIG. The gap between the semiconductor chip 10 and the substrate 20 is sealed and filled with a sealing portion 40 made of a cured product of the adhesive 41. Thus, the semiconductor device 600 is obtained.
- Crimping time may be 5 seconds or less, for example.
- the film adhesive 41 of the present embodiment described above is used, a semiconductor device having excellent connection reliability can be obtained even when the pressure bonding time is 5 seconds or less.
- the semiconductor device is temporarily fixed (in a state where the film-like adhesive for semiconductor is interposed), and heat-treated in a reflow furnace to melt the connection bumps 30 so as to form the semiconductor.
- the chip 10 and the substrate 20 may be connected. Since it is not always necessary to form a metal joint at the temporary fixing stage, it can be crimped with a low load, in a short time, and at a low temperature as compared with the above-mentioned method of crimping while heating. Deterioration of the part can be suppressed.
- the heating temperature is preferably a temperature at which curing of the film adhesive proceeds, and more preferably a temperature at which the film adhesive is completely cured.
- the heating temperature and the heating time are appropriately set.
- the substrate 20 may be connected after the film adhesive 41 is pasted on the semiconductor chip 10.
- a semiconductor film adhesive is supplied onto a semiconductor wafer to which a plurality of semiconductor chips 10 are connected, and then diced into individual pieces, whereby a semiconductor film adhesive is adhered onto the semiconductor chip 10.
- productivity is improved, and generation of voids due to insufficient embedding and a decrease in dicing property can be suppressed.
- connection load is set in consideration of variations in the number and height of the connection bumps 30, the connection bumps 30 due to pressurization, or the amount of deformation of the wiring that receives the bumps in the connection part.
- the connection temperature is preferably such that the temperature of the connection portion is equal to or higher than the melting point of the connection bump 30, but may be any temperature at which metal connection of each connection portion (bump and wiring) is formed.
- connection bump 30 is a solder bump, about 240 ° C. or higher is preferable.
- connection time at the time of connection varies depending on the constituent metal of the connection part, but a shorter time is preferable from the viewpoint of improving productivity.
- connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and even more preferably 5 seconds or less.
- connection time is preferably 60 seconds or less.
- the film-like adhesive for semiconductors of the present embodiment exhibits excellent reflow resistance and connection reliability.
- An epoxy resin, a curing agent, a polymer component, a flux agent, an inorganic filler, and an organic filler in the compounding amount (unit: part by mass) shown in Table 1 are expressed as NV values ([mass content after drying] / [paint before drying).
- the total mass] ⁇ 100) was added to an organic solvent (methyl ethyl ketone) so as to be 60%. Thereafter, the same mass of ⁇ 1.0 mm beads and ⁇ 2.0 mm beads as solid content (epoxy resin, curing agent, flux agent, polymer component, inorganic filler and organic filler) is added, and a bead mill (manufactured by Fritsch Japan Co., Ltd.).
- the mixture was stirred with a planetary pulverizer P-7) for 30 minutes. After stirring, the beads were removed by filtration to prepare a coating varnish containing the first adhesive.
- the obtained coating varnish is coated on a base film (made by Teijin DuPont Films, trade name “Purex A54”) with a small precision coating device (manufactured by Yanai Seiki Co., Ltd.), and a clean oven (ESPEC Co., Ltd.) dried (80 ° C./10 min) and used as the first film as single layer films (A-1), (A-2), (A-3), (A -4) and (A-5) were obtained.
- the thickness of the flux-containing layer in the single layer films (A-1) to (A-5) was 20 ⁇ m.
- the resulting coating varnish was coated on a base film (trade name “Purex A54” manufactured by Teijin DuPont Films Ltd.) with a small precision coating device (Yurui Seiki), and a clean oven (ESPEC Corporation) (Made by company) and dried (80 ° C./10 min), and the second film is a single layer film (B-1), (B-2), (B-3), (B-4) shown in Table 2 , (B-5), (B-6) and (B-7) were obtained.
- the thickness of the flux-free layer in the single layer films (B-1) to (B-7) was 20 ⁇ m.
- melt viscosity of the first adhesive, the second adhesive, and the film-like adhesive (a laminate of a flux-containing layer and a flux-non-containing layer) is measured using a rotary rheometer (TA Instruments, trade name: ARES-G2). ).
- An evaluation sample of the melt viscosity of the film adhesive was prepared by the following procedure. First, two of the single-layer films prepared above (first film and second film) were laminated at 50 ° C. to prepare a two-layer film having a total thickness of 40 ⁇ m. The combinations of single layer films were as shown in Table 3 and Table 4.
- the two-layer film was cut and the cut two-layer films were laminated with each other to produce a four-layer film (laminated film) having a total thickness of 80 ⁇ m.
- the laminated film was cut and laminated with the cut laminated film repeatedly to prepare an evaluation sample having a total thickness of 400 ⁇ m.
- the melt viscosity was measured using the evaluation sample under the following measurement conditions. [Measurement condition] Temperature rising rate: 10 ° C./min Frequency: 10 Hz Temperature range: 30-150 ° C
- the minimum melt viscosity of the first adhesive is 2000 to 4000 Pa ⁇ s (measured value at 130 ° C.)
- the minimum melt viscosity of the second adhesive is 1000 to 3000 Pa ⁇ s (measured value at 120 ° C.).
- the minimum melt viscosity of the film adhesive was 1500 to 3500 Pa ⁇ s (measured value at 130 ° C.).
- the film adhesive produced in the Example or the comparative example was cut out to a predetermined size (length 8 mm ⁇ width 8 mm ⁇ thickness 40 ⁇ m), and the base film without the adhesive layer was peeled off.
- a semiconductor chip with solder bumps (chip size: 7.3 mm long x 7.3 mm wide x 0.15 mm thick, bump height: about 40 ⁇ m in total of copper pillar height and solder height, number of bumps: 328) Laminated.
- the substrate film provided with the adhesive layer was peeled off and the laminated chip was placed on the glass epoxy substrate with copper wiring with the flux-containing layer facing down (thickness of glass epoxy substrate: 420 ⁇ m, thickness of copper wiring: 9 ⁇ m) using a flip mounting apparatus “FCB3” (trade name, manufactured by Panasonic Corporation) (mounting conditions: pressure head temperature 350 ° C., pressure bonding time 3 seconds, pressure bonding pressure 0.5 MPa).
- FCB3 trade name, manufactured by Panasonic Corporation
- connection resistance value of the obtained semiconductor device A was evaluated by measuring the connection resistance value of the obtained semiconductor device A using a multimeter (trade name “R6871E” manufactured by Advantest Corporation).
- the connectivity is “A” (good), and when the connection resistance value is greater than 12.5 ⁇ but not more than 13.5 ⁇ , the connectivity is “B” (defect).
- the connectivity is “C” (defect). All cases where no display was made were evaluated as connectivity “D” (defect).
- the area of the adhesive part on the chip is 100% and the void generation rate is 3% or less, it is “AA” (good), and when it is more than 3% and 5% or less, it is “A” (good).
- the case of more than 10% and 10% or less was evaluated as “B” (defect), and the case of more than 10% was evaluated as “C” (defect).
- solder wettability evaluation Regarding the semiconductor device A manufactured by the above method, the cross section of the connection portion is observed, and when the solder wetting on the upper surface of the Cu wiring is 100% to 50%, “A” (good), and the solder wetting is 50% to 50% The case of 0% was evaluated as “B” (defect), and the case where solder scattering occurred was evaluated as “C” (defect).
- the semiconductor device A produced by the above method is observed with a metal microscope (manufactured by Keyence Corporation) from the upper surface of the device, and the amount of the cured product derived from the film adhesive that protrudes from the periphery (four sides) of the semiconductor chip The width of the part) was measured. The measurement was performed for each side of the semiconductor device, and the average value of the four sides was calculated as the amount of protrusion.
- the bonded semiconductor device B was cured at 175 ° C. for 2 hours in a clean oven (ESPEC Co., Ltd.), and the cured sample was subjected to an accelerated life test device (trade name “PL-422R8” manufactured by Hirayama Seisakusho Co., Ltd.) Conditions: 130 ° C./85% RH / 100 hours, 5 V applied), and the insulation resistance was measured.
- the case where the insulation resistance after 100 hours was 10 8 ⁇ or more was designated as “A”
- the case where 10 7 ⁇ or more and less than 10 8 ⁇ was designated as “B”
- the semiconductor device C was obtained.
- the semiconductor device C after the pressure bonding was cured at 175 ° C. for 2 hours in a clean oven (manufactured by ESPEC Corporation), and the cured sample was subjected to an accelerated life test apparatus (trade name “PL-422R8” manufactured by Hirayama Seisakusho Co., Ltd.) Conditions: 130 ° C./85% RH / 100 hours, 5 V applied), and the insulation resistance was measured.
- the case where the insulation resistance after 100 hours was 10 8 ⁇ or more was designated as “A”
- the case where 10 7 ⁇ or more and less than 10 8 ⁇ was designated as “B”
- SYMBOLS 10 Semiconductor chip, 15 ... Wiring (connection part), 20 ... Board
- Film adhesive 50 ... interposer, 60 ... solder resist, 100, 200, 300, 400, 500, 600 ... semiconductor device.
Abstract
Description
なお、図面中、同一又は相当部分には同一符号を付し、重複する説明は省略する。また、上下左右等の位置関係は、特に断らない限り、図面に示す位置関係に基づくものとする。
さらに、図面の寸法比率は図示の比率に限られるものではない。
本実施形態の半導体用フィルム状接着剤は、フラックス化合物を含有する第1の熱硬化性接着剤(以下、単に「第1の接着剤」ともいう。)からなる第1の層(フラックス含有層)と、第1の層上に設けられ、フラックス化合物を実質的に含有しない第2の熱硬化性接着剤(以下、単に「第2の接着剤」ともいう。)からなる第2の層(フラックス非含有層)と、を備える。
第1の接着剤は、例えば、熱硬化性成分と、フラックス化合物と、を含有する。熱硬化性成分としては、熱硬化性樹脂、硬化剤等が挙げられる。熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂(硬化剤として含有される場合を除く)、ポリイミド樹脂等が挙げられる。これらの中でも、熱硬化性樹脂がエポキシ樹脂であることが好ましい。また、本実施形態の半導体用フィルム状接着剤は、必要に応じて、重量平均分子量が10000以上の高分子成分及びフィラーを含有していてもよい。
エポキシ樹脂としては、分子内に2個以上のエポキシ基を有するものであれば特に制限なく用いることができる。(a)成分として、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂及び各種多官能エポキシ樹脂を使用することができる。これらは単独で又は2種以上の混合物として使用することができる。
(b)成分としては、例えば、フェノール樹脂系硬化剤、酸無水物系硬化剤、アミン系硬化剤、イミダゾール系硬化剤及びホスフィン系硬化剤が挙げられる。(b)成分がフェノール性水酸基、酸無水物、アミン類又はイミダゾール類を含むと、接続部に酸化膜が生じることを抑制するフラックス活性を示し、接続信頼性・絶縁信頼性を向上させることができる。以下、各硬化剤について説明する。
フェノール樹脂系硬化剤としては、分子内に2個以上のフェノール性水酸基を有するものであれば特に制限はなく、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、クレゾールナフトールホルムアルデヒド重縮合物、トリフェニルメタン型多官能フェノール樹脂及び各種多官能フェノール樹脂を使用することができる。これらは単独で又は2種以上の混合物として使用することができる。
酸無水物系硬化剤としては、例えば、メチルシクロヘキサンテトラカルボン酸二無水物、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物及びエチレングリコールビスアンヒドロトリメリテートを使用することができる。これらは単独で又は2種以上の混合物として使用することができる。
アミン系硬化剤としては、例えばジシアンジアミドを使用することができる。
イミダゾール系硬化剤としては、例えば、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノ-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾールトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-ウンデシルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-エチル-4’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体、2-フェニルイミダゾールイソシアヌル酸付加体、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、及び、エポキシ樹脂とイミダゾール類の付加体が挙げられる。これらの中でも、優れた硬化性、保存安定性及び接続信頼性の観点から、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノ-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾールトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-エチル-4’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体、2-フェニルイミダゾールイソシアヌル酸付加体、2-フェニル-4,5-ジヒドロキシメチルイミダゾール及び2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールが好ましい。これらは単独で又は2種以上を併用して用いることができる。また、これらをマイクロカプセル化した潜在性硬化剤としてもよい。
ホスフィン系硬化剤としては、例えば、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラ(4-メチルフェニル)ボレート及びテトラフェニルホスホニウム(4-フルオロフェニル)ボレートが挙られる。
(c)成分は、フラックス活性を有する化合物であり、第1の接着剤において、フラックス剤として機能する。(c)成分としては、はんだ等の表面の酸化膜を還元除去して、金属接合を容易にするものであれば、特に制限なく公知のものを用いることができる。(c)成分としては、フラックス化合物の1種を単独で用いてもよく、フラックス化合物の2種以上を併用してもよい。ただし、(c)成分には、(b)成分である硬化剤は含まれない。
第1の接着剤は、必要に応じて、重量平均分子量が10000以上の高分子成分((d)成分)を含有していてもよい。(d)成分を含有する第1の接着剤は、耐熱性及びフィルム形成性に一層優れる。
検出器:LV4000 UV Detector(株式会社日立製作所製、商品名)
ポンプ:L6000 Pump(株式会社日立製作所製、商品名)
カラム:Gelpack GL-S300MDT-5(計2本)(日立化成株式会社製、商品名)
溶離液:THF/DMF=1/1(容積比)+LiBr(0.03mol/L)+H3PO4(0.06mol/L)
流量:1mL/分
第1の接着剤は、必要に応じて、フィラー((e)成分)を含有していてもよい。(e)成分によって、第1の接着剤の粘度、第1の接着剤の硬化物の物性等を制御することができる。具体的には、(e)成分によれば、例えば、接続時のボイド発生の抑制、第1の接着剤の硬化物の吸湿率の低減等を図ることができる。
第1の接着剤には、酸化防止剤、シランカップリング剤、チタンカップリング剤、レベリング剤、イオントラップ剤等の添加剤を配合してもよい。これらは1種を単独で又は2種以上を組み合わせて用いることができる。これらの配合量については、各添加剤の効果が発現するように適宜調整すればよい。
測定条件
昇温速度:10℃/分
周波数:10Hz
温度範囲:30~150℃
第2の接着剤は、フラックス化合物を実質的に含有しない。「実質的に含有しない」とは、第2の接着剤におけるフラックス化合物の含有量が、第2の接着剤の全質量基準で、0.5質量%未満であることを意味する。
(A)成分は、熱、光、放射線、電気化学的作用等によるラジカルの発生に伴い、ラジカル重合反応が可能である化合物である。(A)成分としては、(メタ)アクリル化合物、ビニル化合物等が挙げられる。(A)成分としては、耐久性、電気絶縁性及び耐熱性に優れる観点から、(メタ)アクリル化合物が好ましい。(メタ)アクリル化合物は、分子内に1個以上の(メタ)アクリル基((メタ)アクリロイル基)を有する化合物であれば特に制限はなく、例えば、ビスフェノールA型、ビスフェノールF型、ナフタレン型、フェノールノボラック型、クレゾールノボラック型、フェノールアラルキル型、ビフェニル型、トリフェニルメタン型、ジシクロペンタジエン型、フルオレン型、アダマンタン型又はイソシアヌル酸型の骨格を含有する(メタ)アクリル化合物;各種多官能(メタ)アクリル化合物(前記骨格を含有する(メタ)アクリル化合物を除く)等を使用することができる。多官能(メタ)アクリル化合物としては、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート等が挙げられる。(A)成分は、1種単独で又は2種以上を併用して用いることができる。
(B)成分としては、(A)成分の硬化剤として機能すれば特に制限はないが、取り扱い性に優れる観点から、熱ラジカル発生剤が好ましい。
第2の接着剤は、高分子成分を更に含有することができる。(C)成分は、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリカルボジイミド樹脂、シアネートエステル樹脂、(メタ)アクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂、アクリルゴム等が挙げられ、その中でも、耐熱性及びフィルム形成性に優れる観点から、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、(メタ)アクリル樹脂、ウレタン樹脂、アクリルゴム、シアネートエステル樹脂及びポリカルボジイミド樹脂からなる群より選ばれる少なくとも1種が好ましく、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、(メタ)アクリル樹脂、ウレタン樹脂及びアクリルゴムからなる群より選ばれる少なくとも1種がより好ましい。(C)成分は、1種単独又は2種以上の混合体又は共重合体として使用することもできる。ただし、(C)成分には、(A)成分に該当する化合物、及び、(D)成分に該当する化合物は含まれない。
第2の接着剤は、粘度又は硬化物の物性を制御するため、及び、半導体チップと基板、若しくは半導体チップ同士を接続した際のボイドの発生又は吸湿率の更なる抑制のために、フィラーを更に含有してもよい。(D)成分としては、第1の接着剤における(e)成分として挙げたフィラーと同様のフィラーを用いることができる。好ましいフィラーの例も同じである。
第2の接着剤には、ラジカル重合性化合物以外の重合性化合物(例えば、カチオン重合性化合物及びアニオン重合性化合物)を配合してもよい。また、第2の接着剤には、第1の接着剤と同様のその他の成分を配合してもよい。これらは1種を単独で又は2種以上を組み合わせて用いることができる。これらの配合量については、各添加剤の効果が発現するように適宜調整すればよい。
硬化反応率(%)=(1-[熱処理後の測定サンプルの発熱量]/[未処理の測定サンプルの発熱量])×100
本実施形態の半導体用フィルム状接着剤は、例えば、第1の層を備える第1のフィルム状接着剤と、第2の層を備える第2のフィルム状接着剤とを用意し、第1の層を備える第1のフィルム状接着剤と、第2の層を備える第2のフィルム状接着剤とを貼り合わせることにより得ることができる。
本実施形態の半導体装置について、図1及び2を用いて以下説明する。図1は、本発明の半導体装置の一実施形態を示す模式断面図である。図1(a)に示すように、半導体装置100は、互いに対向する半導体チップ10及び基板(回路配線基板)20と、半導体チップ10及び基板20の互いに対向する面にそれぞれ配置された配線15と、半導体チップ10及び基板20の配線15を互いに接続する接続バンプ30と、半導体チップ10及び基板20間の空隙に隙間なく充填された接着剤(第1の接着剤及び第2の接着剤)の硬化物からなる封止部40とを有している。半導体チップ10及び基板20は、配線15及び接続バンプ30によりフリップチップ接続されている。配線15及び接続バンプ30は、接着剤の硬化物により封止されており外部環境から遮断されている。封止部40は、第1の接着剤の硬化物を含む上部部分40aと、第2の接着剤の硬化物を含む下部部分40bとを有している。
本実施形態の半導体装置の製造方法について、図4を用いて以下説明する。図4は、本発明の半導体装置の製造方法の一実施形態を模式的に示す図であり、各工程を示す図4(a)、図4(b)及び図4(c)は、半導体装置の断面を示す。
フラックス含有層を備える単層フィルムの作製に使用した化合物を以下に示す。
(a)エポキシ樹脂
・トリフェノールメタン骨格含有多官能固形エポキシ(三菱ケミカル株式会社製、商品名「jER1032H60」)
・ビスフェノールF型液状エポキシ(三菱ケミカル株式会社製、商品名「jERYL983U」)
(b)硬化剤
・2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体(四国化成工業株式会社製、商品名「2MAOK-PW」)
(c)フラックス剤
・グルタル酸(東京化成株式会社製、融点約98℃)
・2-メチルグルタル酸(シグマアルドリッチ社製、融点約78℃)
・3-メチルグルタル酸(東京化成株式会酸、融点約87℃)
(d)高分子成分
・フェノキシ樹脂(新日鉄住金化学株式会社製、商品名「ZX1356-2」、Tg:約71℃、重量平均分子量Mw:約63000)
・フェノキシ樹脂(新日鉄住金化学株式会社製、商品名「FX-293」、Tg:約160℃、重量平均分子量Mw:約40000)
(e)フィラー
・シリカフィラー(株式会社アドマテックス製、商品名「SE2050」、平均粒径:0.5μm)
・エポキシシラン表面処理フィラー(株式会社アドマテックス製、SE2050-SEJ、平均粒径:0.5μm)
・メタクリル表面処理ナノシリカフィラー(株式会社アドマテックス製、商品名「YA100C-MLE」、平均粒径:約100nm)
・メタクリル表面処理ナノシリカフィラー(株式会社アドマテックス、商品名「YA050C-MJE」、平均粒径:約50nm)
・有機フィラー(樹脂フィラー、ロームアンドハースジャパン株式会社製、商品名「EXL-2655」、コアシェルタイプ有機微粒子)
フラックス非含有層を備える単層フィルムの作製に使用した化合物を以下に示す。
・フルオレン型骨格を有するアクリレート(大阪ガスケミカル株式会社、EA-0200、2官能基)
・ビスフェノールA型骨格を有するアクリレート(新中村化学工業株式会社、EA-1020)
・エトキシ化イソシアヌル酸トリアクリレート(新中村化学工業株式会社、A-9300)
・ジクミル過酸化物(日油株式会社、パークミル(登録商標)D)
・ジ-tert-ブチル過酸化物(日油株式会社、パーブチル(登録商標)D)
・1,4-ビス-((tert-ブチルパーオキシ)ジイソプロピル)ベンゼン(日油株式会社、パーブチル(登録商標)P)
・アクリル樹脂(日立化成株式会社、KH-CT-865、重量平均分子量Mw:100000、Tg:10℃)
・ウレタン樹脂(DICコベストロポリマー株式会社、パンデックスT-8175N、Tg:約―23℃)
フラックス含有層を備える単層フィルムの作製に用いたフィラー((e)成分)と同様のフィラーを用いた。
(実施例1~10、並びに比較例1~12)
上記で作製した単層フィルムのうちの2つ(第1のフィルム及び第2のフィルム)を50℃でラミネートし、総厚40μmのフィルム状接着剤を作製した。単層フィルムの組み合わせは、表3及び表4に示すとおりとした。フラックス含有層を備える単層フィルム側の基材フィルムは剥離し、基材フィルムを剥離した面に、フラックス含有層側に粘着層を設けた基材フィルム(6331-00、日立マクセル株式会社製)をラミネートした。比較例1~5では、一方の基材フィルムのみ剥離し、基材フィルムを剥離した面に、上記粘着層を設けた基材フィルム(6331-00、日立マクセル株式会社製)をラミネートした。
(最低溶融粘度の測定)
第1の接着剤、第2の接着剤及びフィルム状接着剤(フラックス含有層とフラックス非含有層との積層体)の溶融粘度を回転式レオメーター(TA Instruments社製、商品名:ARES-G2)を用いて測定した。フィルム状接着剤の溶融粘度の評価サンプルは、以下の手順で作製した。まず、上記で作製した単層フィルムのうちの2つ(第1のフィルム及び第2のフィルム)を50℃でラミネートし、総厚40μmの2層フィルムを作製した。単層フィルムの組み合わせは、表3及び表4に示すとおりとした。その2層フィルムを切断し、切断した2層フィルムを互いに積層することで総厚80μmの4層フィルム(積層フィルム)を作製した。同様の手順で積層フィルムの切断及び切断した積層フィルムのラミネートを繰り返し行い、総厚400μmの評価サンプルを作製した。評価サンプルを用いて下記の測定条件で溶融粘度を測定した。
[測定条件]
昇温速度:10℃/分
周波数:10Hz
温度範囲:30~150℃
以下に示す方法で、実施例及び比較例で得られたフィルム状接着剤及び該フィルム状接着剤を用いて作製した半導体装置について、初期接続性評価、ボイド評価、はんだ濡れ性評価、はみ出し量測定、及び絶縁信頼性評価を行った。結果を表3及び表4に示す。
実施例又は比較例で作製したフィルム状接着剤を所定のサイズ(縦8mm×横8mm×厚さ40μm)に切り抜き、粘着層を備えない基材フィルムを剥離した。はんだバンプ付き半導体チップ(チップサイズ:縦7.3mm×横7.3mm×厚さ0.15mm、バンプ高さ:銅ピラーの高さとはんだの高さの合計で約40μm、バンプ数:328)にラミネートした。粘着層を設けた基材フィルムを剥離し、ラミネートしたチップを、フラックス含有層を下にした状態で、銅配線付きガラスエポキシ基板(ガラスエポキシ基材の厚さ:420μm、銅配線の厚さ:9μm)にフリップ実装装置「FCB3」(パナソニック株式会社製、商品名)で実装した(実装条件:圧着ヘッド温度350℃、圧着時間3秒、圧着圧力0.5MPa)。これにより、図4と同様に上記ガラスエポキシ基板と、はんだバンプ付き半導体チップとがデイジーチェーン接続された半導体装置Aを作製した。
上記の方法で作製した半導体装置Aについて、超音波映像診断装置(商品名「Insight-300」、インサイト株式会社製)により外観画像を撮り、スキャナGT-9300UF(セイコーエプソン株式会社製、商品名)でチップ上の接着剤層(半導体用フィルム状接着剤の硬化物からなる層)の画像を取り込み、画像処理ソフトAdobe Photoshop(登録商標)を用いて、色調補正、二階調化によりボイド部分を識別し、ヒストグラムによりボイド部分の占める割合を算出した。チップ上の接着剤部分の面積を100%として、ボイド発生率が3%以下の場合を「AA」(良好)とし、3%より多く5%以下の場合を「A」(良好)とし、5%より多く10%以下の場合を「B」(不良)とし、10%より多い場合を「C」(不良)として評価した。
上記の方法で作製した半導体装置Aについて、接続部の断面を観察し、Cu配線の上面におけるはんだの濡れが100%~50%の場合を「A」(良好)、はんだの濡れが50%~0%の場合を「B」(不良)、はんだ飛散が発生している場合を「C」(不良)として評価した。
上記の方法で作製した半導体装置Aを該装置の上面から金属顕微鏡(株式会社キーエンス製)で観察し、半導体チップ周辺部(4辺)からはみ出したフィルム状接着剤由来の硬化物の量(はみ出し部分の幅)を測定した。測定は、半導体装置の各辺について行い、4辺の平均値をはみ出し量として算出した。
実施例又は比較例で作製したフィルム状接着剤(厚さ:40μm)を、くし型電極評価TEG(日立化成株式会社製、配線ピッチ:50μm)に貼付し、上部からはんだバンプ付き半導体チップ(チップサイズ:縦7.3mm×横7.3mm×厚さ0.15mm、バンプ高さ:銅ピラーの高さとはんだの高さの合計で約40μm、バンプ数:328)をはんだが付いている面を下向きにした状態でフリップ実装装置「FCB3」(パナソニック株式会社製、商品名)で実装した(実装条件:圧着ヘッド温度350℃、圧着時間3秒、圧着圧力0.5MPaで熱圧着)。これにより半導体装置Bを得た。圧着後の半導体装置Bをクリーンオーブン(ESPEC株式会社製)中、175℃で2時間キュアし、キュア後のサンプルを、加速寿命試験装置(株式会社平山製作所製、商品名「PL-422R8」、条件:130℃/85%RH/100時間、5V印加)に設置し、絶縁抵抗を測定した。100時間後の絶縁抵抗が108Ω以上であった場合を「A」とし、107Ω以上108Ω未満であった場合を「B」とし、107Ω未満であった場合を「C」として評価した。
実施例又は比較例で作製したフィルム状接着剤(厚さ:40μm)を、くし型電極評価TEG(日立化成株式会社製、配線ピッチ:50μm)に貼付し、上部からはんだバンプ付き半導体チップ(チップサイズ:縦7.3mm×横7.3mm×厚さ0.15mm、バンプ高さ:銅ピラーの高さとはんだの高さの合計で約40μm、バンプ数:328)をはんだが付いている面を下向きにした状態でフリップ実装装置「FCB3」(パナソニック株式会社製、商品名)で実装した(実装条件:圧着ヘッド温度180℃、圧着時間3秒、圧着圧力0.5MPaで熱圧着した後(接着剤のゲル化工程)、圧着ヘッド温度を260℃に昇温し、連続的に、圧着ヘッド温度260℃、圧着時間3秒、圧着圧力0.5MPaで熱圧着)。これにより、半導体装置Cを得た。圧着後の半導体装置Cをクリーンオーブン(ESPEC株式会社製)中、175℃で2時間キュアし、キュア後のサンプルを、加速寿命試験装置(株式会社平山製作所製、商品名「PL-422R8」、条件:130℃/85%RH/100時間、5V印加)に設置し、絶縁抵抗を測定した。100時間後の絶縁抵抗が108Ω以上であった場合を「A」とし、107Ω以上108Ω未満であった場合を「B」とし、107Ω未満であった場合を「C」として評価した。
Claims (14)
- フラックス化合物を含有する第1の熱硬化性接着剤からなる第1の層と、
前記第1の層上に設けられ、フラックス化合物を実質的に含有しない第2の熱硬化性接着剤からなる第2の層と、を備える、半導体用フィルム状接着剤。 - 前記第2の熱硬化性接着剤は、200℃で5秒間保持したときの硬化反応率が80%以上である、請求項1に記載の半導体用フィルム状接着剤。
- 前記第2の熱硬化性接着剤は、ラジカル重合性化合物と熱ラジカル発生剤とを含有する、請求項1又は2に記載の半導体用フィルム状接着剤。
- 前記熱ラジカル発生剤は過酸化物である、請求項3に記載の半導体用フィルム状接着剤。
- 前記ラジカル重合性化合物は(メタ)アクリル化合物である、請求項3又は4に記載の半導体用フィルム状接着剤。
- 前記(メタ)アクリル化合物はフルオレン型骨格を有する、請求項5に記載の半導体用フィルム状接着剤。
- 前記フラックス化合物はカルボキシル基を有する、請求項1~6のいずれか一項に記載の半導体用フィルム状接着剤。
- 前記フラックス化合物は2つ以上のカルボキシル基を有する、請求項1~7のいずれか一項に記載の半導体用フィルム状接着剤。
- 前記フラックス化合物の融点は150℃以下である、請求項1~9のいずれか一項に記載の半導体用フィルム状接着剤。
- 前記第1の熱硬化性接着剤は硬化剤を含有する、請求項1~10のいずれか一項に記載の半導体用フィルム状接着剤。
- 前記硬化剤はイミダゾール系硬化剤である、請求項11に記載の半導体用フィルム状接着剤。
- 半導体チップ及び配線回路基板のそれぞれの接続部が互いに電気的に接続された半導体装置、又は、複数の半導体チップのそれぞれの接続部が互いに電気的に接続された半導体装置の製造方法であって、
前記接続部の少なくとも一部を、請求項1~12のいずれか一項に記載の半導体用フィルム状接着剤を用いて封止する工程を備える、半導体装置の製造方法。 - 半導体チップ及び配線回路基板のそれぞれの接続部が互いに電気的に接続された半導体装置、又は、複数の半導体チップのそれぞれの接続部が互いに電気的に接続された半導体装置であって、
前記接続部の少なくとも一部が、請求項1~12のいずれか一項に記載の半導体用フィルム状接着剤の硬化物によって封止されている、半導体装置。
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