WO2019167460A1 - 半導体用接着剤及びそれを用いた半導体装置の製造方法 - Google Patents
半導体用接着剤及びそれを用いた半導体装置の製造方法 Download PDFInfo
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- WO2019167460A1 WO2019167460A1 PCT/JP2019/001342 JP2019001342W WO2019167460A1 WO 2019167460 A1 WO2019167460 A1 WO 2019167460A1 JP 2019001342 W JP2019001342 W JP 2019001342W WO 2019167460 A1 WO2019167460 A1 WO 2019167460A1
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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
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy 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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/07—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L29/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/18—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different subgroups of the same main group of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N
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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
- C09J2301/30—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
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16245—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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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 disclosure relates to a semiconductor adhesive and a method for manufacturing a semiconductor device using the same.
- Flip chip connection methods include metal bonding using solder, tin, gold, silver, copper, etc., metal bonding by applying ultrasonic vibration, method of maintaining mechanical contact by the shrinkage force of the resin, etc.
- a method of metal bonding using solder, tin, gold, silver, copper, or the like is common.
- a COB (Chip On Board) type connection method that is widely used in BGA (Ball Grid Array), CSP (Chip Size Package), etc. is also a flip chip connection method.
- the flip chip connection method is also widely used in a COC (Chip On Chip) type connection method in which connection portions (bumps or wirings) are formed on a semiconductor chip and connected between the semiconductor chips (for example, See Patent Document 1 below).
- the present disclosure controls a resin shape that protrudes when a chip is mounted, and a resin that protrudes in a shape along the side surface of the chip so that a semiconductor device that does not have a resin shortage when mounted can be obtained, and a semiconductor using the same
- the main object is to provide a method of manufacturing a device.
- One aspect of the present disclosure is [1] a semiconductor device in which electrodes of respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or electrodes of respective connection portions of a plurality of semiconductor chips.
- a semiconductor adhesive used for sealing at least a part of the connection portion wherein the thixotropic value of the semiconductor adhesive is 1.0 or more, 3.1
- the above thixotropy values are obtained when the frequency is continuously changed from 1 Hz to 70 Hz with a shear viscosity measuring device at a constant temperature of 120 ° C. for a sample in which the semiconductor adhesive is laminated to a thickness of 400 ⁇ m.
- Is an adhesive for semiconductors which is a value obtained by dividing the viscosity value at 7 Hz by the viscosity value at 70 Hz.
- another aspect of the present disclosure includes [2] (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a weight average molecular weight of 10,000 or more. It is an adhesive for semiconductors.
- Another aspect of the present disclosure is [3] the semiconductor adhesive according to [2], further including (d) a filler.
- Another aspect of the present disclosure is the semiconductor adhesive according to [2] or [3], further including [4] and (e) a flux agent.
- Another aspect of the present disclosure is the semiconductor adhesive according to any one of the above [1] to [6], which is [7] film-like.
- [8] the semiconductor adhesive according to any one of [1] to [7] is used, and the semiconductor chip and the wiring circuit are connected via the semiconductor adhesive by a connection device.
- the substrates are aligned, connected to each other, the electrodes of the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other, and at least a part of the connection portions is sealed with the adhesive for semiconductor.
- the shape of the resin protruding to the outer periphery of the chip when the semiconductor device is mounted is controlled, and the resin runs out in a shape along the side surface of the chip. Can be suppressed. Further, according to the present disclosure, it is possible to provide a semiconductor device using such a semiconductor adhesive and a method for manufacturing the same.
- FIG. 5 is a schematic cross-sectional view showing another embodiment of a semiconductor device according to the present disclosure.
- FIG. 5 is a schematic cross-sectional view showing another embodiment of a semiconductor device according to the present disclosure.
- FIG. 5 is a schematic cross-sectional view showing another embodiment of a semiconductor device according to the present disclosure.
- FIG. 5 is a schematic cross-sectional view showing another embodiment of a semiconductor device according to the present disclosure.
- a 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 upper limit value or lower limit value of a numerical range of a certain step can be arbitrarily combined with the upper limit value or lower limit value of the numerical range of another step.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- “A or B” only needs to include either A or B, and may include both.
- the materials exemplified in this specification can be used alone or in combination of two or more.
- “(meth) acryl” means acryl or methacryl corresponding thereto.
- the adhesive for a semiconductor according to the present embodiment is a semiconductor device in which electrodes of respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or electrodes of respective connection portions of a plurality of semiconductor chips. Are used for sealing at least a part of the connecting portion.
- the thixotropic value of the adhesive for semiconductor according to this embodiment is 1.0 or more and 3.1 or less.
- the thixotropy value is a value obtained by measuring the viscosity when the frequency is continuously changed from 1 Hz to 70 Hz with a shear viscosity measuring device at a constant temperature of 120 ° C. for a sample obtained by laminating the semiconductor adhesive to a thickness of 400 ⁇ m.
- the viscosity value at 7 Hz is divided by the viscosity value at 70 Hz.
- the thixotropy value may be 1.5 or more, 2.0 or more, or 2.5 or more.
- the semiconductor adhesive according to the present embodiment may contain (a) an epoxy resin, (b) a curing agent, (c) a high molecular weight component having a weight average molecular weight of 10,000 or more, and (d) a filler, (e ) It is preferable to contain a flux agent.
- the epoxy resin of component (a) include epoxy resins having two or more epoxy groups in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, A cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene type epoxy resin, various polyfunctional epoxy resins, and the like can be used.
- a component can be used individually by 1 type or in combination of 2 or more types.
- the content of the component (a) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, still more preferably 20 to 40% by mass based on the total solid content of the semiconductor adhesive. is there.
- the content of the component (a) is 10% by mass or more, it is easy to sufficiently control the flow of the resin after curing, and when it is 50% by mass or less, the resin component of the cured product does not increase excessively, Easy to reduce warpage.
- the semiconductor adhesive according to this embodiment contains (b) a curing agent.
- a curing agent examples include a phenol resin curing agent, an acid anhydride curing agent, an amine curing agent, an imidazole curing agent, and a phosphine curing agent.
- the component contains a phenolic hydroxyl group, acid anhydride, amines or imidazoles, it is easy to show flux activity that suppresses the formation of an oxide film at the connection part, and the connection reliability and insulation reliability are easily improved. Can be made.
- each curing agent will be described.
- Phenolic resin-based curing agent includes a curing agent having two or more phenolic hydroxyl groups in the molecule.
- Formaldehyde polycondensates, triphenylmethane type polyfunctional phenol resins, various polyfunctional phenol resins, and the like can be used.
- curing agent can be used individually by 1 type or in combination of 2 or more types.
- the equivalent ratio (phenolic hydroxyl group / epoxy group, molar ratio) of the phenol resin-based curing agent to the component (a) is preferably 0.3 to 1.5 from the viewpoint of excellent curability, adhesiveness, and storage stability. 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is more preferable. If the equivalent 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, the unreacted phenolic hydroxyl group does not remain excessively, and the water absorption rate However, the insulation reliability tends to be further improved.
- the acid anhydride curing agent includes methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis Anhydro trimellitate and the like can be used.
- curing agent can be used individually by 1 type or in combination of 2 or more types.
- the equivalent ratio of the acid anhydride curing agent to the component (a) is 0.3 to 1.5 from the viewpoint of excellent curability, adhesiveness, and storage stability. Is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is more preferable. If the equivalent ratio is 0.3 or more, the curability tends to be improved and the adhesive force tends to be improved. If the equivalent ratio is 1.5 or less, the unreacted acid anhydride does not remain excessively, and the water absorption rate However, the insulation reliability tends to be further improved.
- (B-iii) Amine Curing Agent As the amine curing agent, dicyandiamide, various amine compounds and the like can be used.
- the equivalent ratio of the amine curing agent to the component (a) is preferably 0.3 to 1.5 from the viewpoint of excellent curability, adhesiveness and storage stability, To 1.0 is more preferable, and 0.5 to 1.0 is more preferable.
- the equivalence ratio is 0.3 or more, the curability is improved and the adhesive force tends to be improved.
- the equivalent ratio is 1.5 or less, the unreacted amine does not remain excessively, and the insulation reliability is improved. There is a tendency to further improve.
- imidazole type curing agent examples include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzylimidazole, 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
- 1-cyanoethyl-2-undecylimidazole 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimelli, from the viewpoint of further improving curability, storage stability and connection reliability.
- 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). If the content of the imidazole-based curing agent is 0.1 parts by mass or more, the curability tends to be improved, and if it is 20 parts by mass or less, the adhesive composition is cured before metal bonding is formed. There is a tendency that poor connection is unlikely to occur.
- Phosphine curing agent examples include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate. Is mentioned.
- 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).
- the content of the phosphine-based curing agent is 0.1 parts by mass or more, curability tends to be improved, and when it is 10 parts by mass or less, the adhesive for a semiconductor is cured before a metal bond is formed. There is a tendency that poor connection is unlikely to occur.
- the phenol resin-based curing agent, the acid anhydride-based curing agent, and the amine-based curing agent can be used singly or in combination 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 component (b) from the viewpoint of excellent curability, a combined use of a phenol resin curing agent and an imidazole curing agent, a combined use of an acid anhydride curing agent and an imidazole curing agent, an amine curing agent and an imidazole curing agent.
- the imidazole curing agent alone is preferably used. Since productivity improves when connected in a short time, it is more preferable to use an imidazole-based curing agent excellent in rapid curability. In this case, since volatile components such as low molecular components can be suppressed when cured in a short time, the generation of voids can be easily suppressed.
- ((C) component high molecular weight component having a weight average molecular weight of 10,000 or more)
- phenoxy resin, polyimide resin, (Meth) acrylic resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin are preferable, and phenoxy resin, polyimide resin, (meth) acrylic resin, and acrylic rubber are more preferable.
- the component (c) can be used alone or as a mixture or copolymer of two or more.
- the mass ratio of the component (c) to the component (a) is not particularly limited, but in order to maintain the film shape, the content of the component (a) is 0 with respect to 1 part by mass of the component (c).
- the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass.
- a thixotropy value can be adjusted also with the combination of (c) component and (a) component, and those mass ratios.
- the weight average molecular weight of the component (c) is 10000 or more in terms of polystyrene, but preferably 30000 or more, more preferably 40000 or more, and further preferably 50000 or more in order to exhibit good film formability alone.
- the weight average molecular weight is 10,000 or more, there is no possibility that the film formability is lowered.
- the weight average molecular weight means a weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).
- the polydispersity Mw / Mn of the component (c) is preferably 3 or less, and more preferably 2.5 or less.
- Mw / Mn is 3 or less, it is considered that there is a tendency that the thixotropy value tends to be low with little variation in molecular weight.
- component (d) component filler
- the filler of component (d) include an insulating inorganic filler.
- an inorganic filler having an average particle size of 100 nm or less is more preferable.
- the insulating inorganic filler include glass, silica, alumina, titanium oxide, mica, boron nitride, and the like. Among them, silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and boron nitride are more preferable.
- the insulating inorganic filler may be a whisker, and examples of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.
- An insulating inorganic filler can be used individually by 1 type or in combination of 2 or more types.
- the shape, particle size, and content of the component (d) are not particularly limited.
- the component (d) is preferably insulative. It is preferable that the semiconductor adhesive according to the present embodiment does not contain a conductive metal filler such as a silver filler or a solder filler.
- the component (d) is preferably a filler subjected to surface treatment from the viewpoint of improving dispersibility and adhesive strength.
- the surface treatment agent glycidyl (epoxy) compounds (excluding compounds corresponding to the component (a)), amine compounds, phenyl compounds, phenylamino compounds, (meth) acrylic compounds (for example, the following general compounds) A compound having a structure represented by the formula (1)), a vinyl compound having a structure represented by the following general formula (2), and the like.
- R 11 represents a hydrogen atom or an alkyl group
- R 12 represents an alkylene group
- the filler surface-treated with the compound having the structure represented by the general formula (1) includes an acrylic surface-treated filler in which R 11 is a hydrogen atom, a methacrylic surface-treated filler in which R 11 is a methyl group, and R 11 is ethyl.
- the ethacryl surface treatment filler which is a base, is included. From the viewpoint of reactivity with the resin contained in the semiconductor adhesive and the surface of the semiconductor substrate and bond formation, R 11 is not bulky.
- a surface treatment filler is preferred.
- R 12 is not particularly limited, but a higher weight average molecular weight is preferable because it contains fewer volatile components.
- R 21 , R 22 and R 23 represent a monovalent organic group, and R 24 represents an alkylene group.
- R 21 , R 22 and R 23 are preferably groups that are not relatively bulky, and may be, for example, a hydrogen atom or an alkyl group.
- R 21 , R 22 and R 23 may be a monovalent organic group that improves the reactivity of the vinyl group.
- R 24 is not particularly limited, but is preferably higher in weight average molecular weight from the viewpoint that voids are less likely to volatilize and can easily reduce voids.
- R 21 , R 22 , R 23 and R 24 may be selected depending on the ease of surface treatment.
- silane treatment agents such as epoxy silane, amino silane, (meth) acrylic silane and the like are preferable because of easy surface treatment.
- glycidyl, phenylamino, and (meth) acrylic compounds are preferable from the viewpoint of excellent dispersibility, fluidity, and adhesive strength.
- phenyl and (meth) acrylic compounds are more preferable from the viewpoint of excellent storage stability.
- the average particle diameter of the component (d) is preferably 100 nm or less and more preferably 60 nm or less from the viewpoint of improving visibility.
- the component (d) is preferably an inorganic filler having an average particle size of 60 nm or less that has been surface-treated with (meth) acrylic silane or epoxy silane from the viewpoint of improving adhesive strength.
- the thixotropy value tends to decrease as the average particle size of the component (d) increases.
- the content of the component (d) is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and further preferably 50 to 75% by mass based on the total amount of the adhesive for semiconductor.
- the content of the component (d) is 20% by mass or more, there is no possibility that the adhesive strength is lowered or the reflow resistance is lowered.
- the content of the component (d) is 40% by mass or less, there is no fear that connection reliability is lowered due to thickening. As the content of the component (d) is larger, the thixotropy value tends to be smaller.
- the semiconductor adhesive may further contain (e) a fluxing agent exhibiting flux activity (activity for removing oxides, impurities, etc.).
- a fluxing agent exhibiting flux activity (activity for removing oxides, impurities, etc.).
- the fluxing agent include nitrogen-containing compounds having an unshared electron pair (imidazoles, amines, etc., except for those contained in the component (b)), carboxylic acids, phenols, and alcohols.
- carboxylic acid expresses flux activity strongly, and it is easy to improve connectivity.
- the content of the component (e) is preferably 0.2 to 3% by mass, preferably 0.4 to 1.8% by mass, based on the total solid content of the adhesive for semiconductors, from the viewpoint of solder wettability. It is more preferable that
- the semiconductor adhesive may further contain an ion trapper, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and the like. These may be used singly or in combination of two or more. About these compounding quantities, what is necessary is just to adjust suitably so that the effect of each additive may express.
- the semiconductor adhesive according to this embodiment is preferably in the form of a film (film adhesive) from the viewpoint of improving productivity.
- a method for producing the film adhesive will be described below.
- the resin varnish is prepared by adding the component (a), the component (b), the component (c), and other components, if necessary, to an organic solvent and then dissolving or dispersing them by stirring, mixing, kneading, or the like. . Then, after applying the resin varnish using a knife coater, roll coater, applicator, die coater, comma coater, etc. on the base film subjected to the release treatment, the organic solvent is reduced by heating, and the base film A film adhesive is formed thereon. Further, before reducing the organic solvent by heating, a film adhesive may be formed on the wafer by a method of drying the solvent after spin-coating a resin varnish on the wafer or the like to form a film.
- 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.
- cyclohexanone it is preferable to use cyclohexanone, and it is preferable that part or all of the material contained in the semiconductor adhesive is soluble in cyclohexanone. That is, part or all of the material contained in the resin varnish is preferably a cyclohexanone dissolved material.
- 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 is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions when the organic solvent is volatilized.
- the polyester film, the polypropylene film, the polyethylene terephthalate film, the polyimide film, the polyetherimide film, the poly Examples include ether naphthalate film and methylpentene film.
- the base film is not limited to a single layer composed of one of these films, and may be a multilayer film composed of two or more films.
- the conditions for volatilizing the organic solvent from the resin varnish after application specifically, heating at 50 to 200 ° C. for 0.1 to 90 minutes is preferable. As long as there is no effect on voids and viscosity adjustment after mounting, it is preferable that the organic solvent is volatilized to 1.5% by mass or less.
- the film thickness of the film-like adhesive according to this embodiment is preferably 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m from the viewpoints of visibility, fluidity, and fillability.
- the adhesive for a semiconductor according to the present embodiment is suitably used for a semiconductor device, and is preferable as an adhesive for a semiconductor.
- the electrodes of the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other.
- it is particularly preferably used for sealing the connection portion.
- a semiconductor device using the semiconductor adhesive according to the present embodiment will be described.
- the electrodes of the connection part in the semiconductor device may be either metal bonding between the bump and the wiring or metal bonding between the bump and the bump.
- flip-chip connection that obtains electrical connection via a semiconductor adhesive may be used.
- FIG. 1 is a schematic sectional view showing an embodiment of a semiconductor device (COB type connection mode of a semiconductor chip and a substrate).
- the first semiconductor device 100 is disposed on the semiconductor chip 10 and the substrate (wiring circuit board) 20 facing each other and on the surfaces facing each other of the semiconductor chip 10 and the substrate 20, respectively.
- the wiring 15 includes connection bumps 30 that connect the semiconductor chip 10 and the wiring 15 of the substrate 20 to each other, and an adhesive 40 that is filled in the gap between the semiconductor chip 10 and the substrate 20 without any gaps.
- 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 semiconductor adhesive 40 and are shielded from the external environment.
- the second semiconductor device 200 is disposed on the semiconductor chip 10 and the substrate (wiring circuit board) 20 facing each other and on the surfaces facing each other of the semiconductor chip 10 and the substrate 20, respectively.
- the bump 32 and the semiconductor adhesive 40 filled in the gap between the semiconductor chip 10 and the substrate 20 without a gap are provided.
- 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 semiconductor adhesive 40 and are shielded from the external environment.
- FIG. 2 is a schematic cross-sectional view showing another embodiment of a semiconductor device (COC type connection mode between semiconductor chips).
- the third semiconductor device 300 is the same as the first semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wirings 15 and connection bumps 30. is there.
- the fourth semiconductor device 400 is the same as the second 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 various semiconductors such as elemental semiconductors composed of the same kind of elements such as silicon and germanium, and compound semiconductors such as gallium / arsenic and indium / phosphorus can be used.
- the substrate 20 is not particularly limited as long as it is a printed circuit board, and is formed on the surface of an insulating substrate mainly composed of glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin, or the like.
- Circuit board on which wiring (wiring pattern) is formed by etching away unnecessary portions of the metal layer, circuit board on which wiring (wiring pattern) is formed on the surface of the insulating substrate by metal plating, etc., surface of the insulating substrate A circuit board on which a conductive material is printed and wiring (wiring pattern) is formed can be used.
- Connections such as wiring 15 and bumps 32 are made of gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), nickel, tin, lead, etc. And may contain a plurality of metals.
- the surface of the wiring is mainly composed of gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc.
- a metal layer may be formed. This metal layer may be composed of only a single component or may be composed of a plurality of components. Moreover, you may have the structure where the some metal layer was laminated
- the main components are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. May be used, and may be composed of only a single component or may be composed of a plurality of components. Moreover, you may form so that the structure where these metals were laminated
- the bump may be formed on a semiconductor chip or a substrate. Copper and solder are generally used because they are inexpensive. Since copper and solder contain oxides, impurities, and the like, the adhesive for semiconductor preferably has flux activity.
- an adhesive may be flip-chip connected or stacked between semiconductor chips to form a hole penetrating the semiconductor chip and connected to the electrode on the pattern surface.
- FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device (semiconductor chip laminated type (TSV)).
- TSV semiconductor chip laminated type
- 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 connected. Is flip-chip connected.
- the gap between the semiconductor chip 10 and the interposer 50 is filled with the semiconductor adhesive 40 without any gaps.
- the semiconductor chip 10 is repeatedly stacked via the wiring 15, the connection bumps 30, and the semiconductor adhesive 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.
- electrodes 34 filled in holes that penetrate the inside of the semiconductor chip 10.
- copper, aluminum, etc. can be used as a material of the penetration electrode 34.
- the through electrode 34 passes vertically through the semiconductor chip 10, the distance between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 can be shortened and flexible connection is possible.
- the semiconductor adhesive according to the present embodiment is suitably used as a sealing material between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 in such a TSV technology.
- the semiconductor device manufacturing method connects a semiconductor chip and a printed circuit board or a plurality of semiconductor chips using the semiconductor adhesive according to the present embodiment.
- the semiconductor chip and the printed circuit board are connected to each other via an adhesive, and the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other.
- connection portions can be connected to each other by metal bonding. That is, the connection portions of the semiconductor chip and the printed circuit board are connected to each other by metal bonding, or the connection portions of the plurality of semiconductor chips are connected to each other by metal bonding.
- a substrate for example, a glass epoxy substrate
- a semiconductor chip 10 having a wiring (for example, copper pillars, copper posts) 15 are interposed via a semiconductor adhesive 40.
- the wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are electrically connected by connection bumps (solder bumps) 30.
- a solder resist 70 is disposed on the surface of the substrate 60 where the wiring 15 is formed, except for the position where the connection bump 30 is formed.
- a semiconductor adhesive (film adhesive or the like) 40 is stuck on the substrate 60 on which the solder resist 70 is formed. Affixing can be performed by a hot press, roll lamination, vacuum lamination, or the like. The supply area and thickness of the semiconductor adhesive 40 are appropriately set depending on the size of the semiconductor chip 10 or the substrate 60, the bump height, and the like.
- the semiconductor adhesive 40 may be affixed to the semiconductor chip 10, and the semiconductor adhesive 40 is affixed by dicing and dicing into pieces after the semiconductor adhesive 40 is affixed to the semiconductor wafer.
- the semiconductor chip 10 may be manufactured.
- the adhesive for semiconductor has a high light transmittance, the visibility is ensured even if the alignment mark is covered. Therefore, there is a range to be applied not only on the semiconductor wafer (semiconductor chip) but also on the substrate. It is not limited and is easy to handle.
- connection bumps 30 on the wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are aligned using a connection device such as a flip chip bonder. To do. Then, the semiconductor chip 10 and the substrate 60 are pressed while being heated at a temperature equal to or higher than the melting point of the connection bump 30 (when solder is used for the connection portion, it is preferable that a temperature of 240 ° C. or higher is applied to the solder portion). 10 and the substrate 60 are connected, and the gap between the semiconductor chip 10 and the substrate 60 is sealed and filled with the semiconductor adhesive 40.
- connection load depends on the number of bumps, but is set in consideration of absorption of bump height variation, control of the amount of bump deformation, and the like.
- the connection time is preferably a short time from the viewpoint of improving productivity. It is preferable to melt the solder, remove the oxide film, surface impurities, etc., and form a metal joint at the connection.
- the short connection time means that a time during which a temperature of 240 ° C. or higher is applied to the connecting portion during the connection formation (final pressing) (for example, time when using solder) is 10 seconds or less.
- the connection time is preferably 5 seconds or less, and more preferably 3 seconds or less.
- the semiconductor device may be manufactured by temporarily fixing and melting the solder bumps by heat treatment in a reflow furnace and connecting the semiconductor chip and the substrate. Temporary fixing does not require the necessity of forming a metal bond, so it can have lower load, shorter time, and lower temperature than the above-mentioned main pressure bonding, and there are merits such as improvement of productivity and prevention of deterioration of connection parts. .
- the adhesive may be cured by performing a heat treatment in an oven or the like.
- the heating temperature is a temperature at which the curing of the adhesive proceeds, and preferably almost completely.
- the heating temperature and the heating time may be set as appropriate.
- the obtained semiconductor device includes a cured product of the adhesive.
- Epoxy resin / Trifunctional methane skeleton-containing polyfunctional solid epoxy resin (Mitsubishi Chemical Corporation, trade name “EP1032H60”, hereinafter referred to as “EP1032”) ⁇ Naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, trade name “HP4032D”) -Bisphenol F type liquid epoxy resin (Mitsubishi Chemical Corporation, trade name “YL983U”, hereinafter referred to as “YL983”) -Flexible epoxy resin (Mitsubishi Chemical Corporation, trade name “YL7175”, hereinafter referred to as “YL7175”)
- Inorganic silica filler manufactured by Admatechs Co., Ltd., trade name “SE2050”, average particle size: 0.5 ⁇ m, hereinafter referred to as “SE2050”
- Inorganic silica filler manufactured by Admatechs Co., Ltd., trade name “SE2050SEJ”, average particle size: 0.5 ⁇ m, hereinafter referred to as “SE2050SEJ”
- Example 1 11.25 g of epoxy resin (6.8 g of “EP1032”, 0.75 g of “HP4032D”, 1.5 g of “YL983”, 2.2 g of “YL7175”), 0.6 g of curing agent “2MAOK”, glutaric acid 0.45 g, 35.3 g of inorganic filler “SE nanosilica”, 2.0 g of acrylic resin “LA4285”, and cyclohexanone (in which the amount of solid content in the resin varnish becomes 47% by mass) are charged with a diameter of 1.0 mm.
- the obtained resin varnish was coated on a base film (manufactured by Teijin DuPont Films, trade name “Purex A54”) with a small precision coating device (manufactured by Yasui Seiki Co., Ltd.).
- the varnish was dried (100 ° C./5 minutes) in a clean oven (manufactured by Espec Co., Ltd.) to obtain a film adhesive.
- the thickness was made to be 0.02 mm.
- Example 2 A film adhesive was prepared in the same manner as in Example 1 except that the epoxy resin “HP4032D” was increased to 1.5 g and the epoxy resin “YL983” was decreased to 0.75 g.
- Example 1 Example except that 2.3 g of inorganic silica filler (trade name “SE2050”, average particle size: 0.5 ⁇ m) manufactured by Admatechs Co., Ltd. was added without adding epoxy resins “YL7175” and “HP4032D”. In the same manner as in Example 1, a film adhesive was produced.
- inorganic silica filler trade name “SE2050”, average particle size: 0.5 ⁇ m
- Example 2 Comparative Example 2 Add 3.3 g of inorganic silica filler (manufactured by Admatechs Co., Ltd., trade name “SE2050SEJ”, average particle size: 0.5 ⁇ m), reduce “SE nanosilica” to 27.9 g, and reduce “LA4285” to 0.5 g A film adhesive was produced in the same manner as in Example 1 except that.
- inorganic silica filler manufactured by Admatechs Co., Ltd., trade name “SE2050SEJ”, average particle size: 0.5 ⁇ m
- Table 1 summarizes the formulations of Examples 1 and 2 and Comparative Examples 1 and 2.
- the semiconductor device obtained by the above (3) semiconductor device manufacturing method is observed from above the upper chip with a microscope (manufactured by Keyence Corporation), and the resin protrudes from the end of the chip. The width was measured.
- the protruding width is the protruding width W 1 (unit: ⁇ m) of the resin from the center of one side of the chip and the protruding width W of the resin from the center side of 0.2 mm from one end (corner of the chip) of the one side. 2 (unit: ⁇ m) was measured, and the ratio (W 2 / W 1 ) between the two was determined.
- W 2 is the protruding width resins from the position of 0.2mm center side from one end of the one side of the chip, and, among the protruding width of the resin from the position of 0.2mm center side from the other end, a small Is the value of This ratio (W 2 / W 1 ) was measured for all four sides of the chip, and the average value was determined as “coverage”.
- Coverability is an index indicating whether the adhesive resin has spread to the corners of the chip in the semiconductor device. Since it is preferable that there is no difference in the protrusion width between the corner portion and the center portion of the side of the semiconductor device, the closer the coverage is to 1, the better.
- Table 1 shows the results of thixotropy measurement and coverage evaluation.
- Example 1 and Example 2 with a thixotropy value of 3.1 or less had a coverage of more than 0.4, but Comparative Example 1 with a greater thixotropy value of more than 3.1 was compared. In Example 2, the coverage was less than 0.4. From these things, it was confirmed that according to the film-like adhesive for semiconductors of the present disclosure having a low thixotropy value, the coverage is improved.
- SYMBOLS 10 Semiconductor chip, 15 ... Wiring, 20, 60 ... Board
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Abstract
Description
本実施形態に係る半導体用接着剤は、半導体チップ及び配線回路基板のそれぞれの接続部の電極同士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の電極同士が互いに電気的に接続された半導体装置において、上記接続部の少なくとも一部の封止に用いられる。
(a)成分の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エポキシ樹脂が挙げられ、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、各種多官能エポキシ樹脂等を使用することができる。(a)成分は、1種単独で又は2種以上を組み合わせて用いることができる。
本実施形態に係る半導体用接着剤は、(b)硬化剤を含有する。硬化剤としては、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等が挙げられる。(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やすく、接続信頼性・絶縁信頼性を容易に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硬化剤が挙げられ、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、各種多官能フェノール樹脂等を使用することができる。フェノール樹脂系硬化剤は、1種単独で又は2種以上を組み合わせて用いることができる。
酸無水物系硬化剤としては、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、エチレングリコールビスアンヒドロトリメリテート等を使用することができる。酸無水物系硬化剤は、1種単独で又は2種以上を組み合わせて用いることができる。
アミン系硬化剤としては、ジシアンジアミド、各種アミン化合物等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、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、エポキシ樹脂とイミダゾール類の付加体等が挙げられる。これらの中でも、硬化性、保存安定性及び接続信頼性にさらに優れる観点から、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。イミダゾール系硬化剤は、1種単独で又は2種以上を組み合わせて用いることができる。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、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)ボレート等が挙げられる。
(c)重量平均分子量10000以上の高分子量成分((a)成分に該当する化合物を除く)としては、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、ポリウレタン樹脂、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、フェノキシ樹脂、ポリイミド樹脂、(メタ)アクリル樹脂、アクリルゴム、シアネートエステル樹脂、ポリカルボジイミド樹脂が好ましく、フェノキシ樹脂、ポリイミド樹脂、(メタ)アクリル樹脂、アクリルゴムがより好ましい。(c)成分は、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。
(d)成分のフィラーとしては、絶縁性無機フィラー等が挙げられる。中でも、平均粒径100nm以下の無機フィラーであればより好ましい。絶縁性無機フィラーとしては、ガラス、シリカ、アルミナ、酸化チタン、マイカ、窒化ホウ素等が挙げられ、その中でも、シリカ、アルミナ、酸化チタン、窒化ホウ素が好ましく、シリカ、アルミナ、窒化ホウ素がより好ましい。絶縁性無機フィラーは、ウィスカーであってもよく、ウィスカーとしては、ホウ酸アルミニウム、チタン酸アルミニウム、酸化亜鉛、珪酸カルシウム、硫酸マグネシウム、窒化ホウ素等が挙げられる。絶縁性無機フィラーは、1種単独で又は2種以上を組み合わせて用いることができる。(d)成分の形状、粒径、及び含有量は特に制限されない。
半導体用接着剤は、フラックス活性(酸化物、不純物等を除去する活性)を示す(e)フラックス剤をさらに含有することができる。フラックス剤としては、非共有電子対を有する含窒素化合物(イミダゾール類、アミン類等。ただし、(b)成分に含まれるものを除く)、カルボン酸類、フェノール類及びアルコール類が挙げられる。なお、アルコール類に比べてカルボン酸類の方がフラックス活性を強く発現し、接続性を向上し易い。
本実施形態に係る半導体用接着剤は、生産性が向上する観点から、フィルム状(フィルム状接着剤)であることが好ましい。フィルム状接着剤の作製方法を以下に説明する。
本実施形態に係る半導体用接着剤は、半導体装置に好適に用いられ、半導体用接着剤として好適であり、半導体チップ及び配線回路基板のそれぞれの接続部の電極同士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の電極同士が互いに電気的に接続された半導体装置において接続部の封止に特に好適に用いられる。以下、本実施形態に係る半導体用接着剤を用いた半導体装置について説明する。半導体装置における接続部の電極同士は、バンプと配線との金属接合、及び、バンプとバンプとの金属接合のいずれでもよい。半導体装置では、例えば、半導体用接着剤を介して電気的な接続を得るフリップチップ接続が用いられてよい。
本実施形態に係る半導体装置の製造方法は、本実施形態に係る半導体用接着剤を用いて、半導体チップ及び配線回路基板、又は、複数の半導体チップ同士を接続する。本実施形態に係る半導体装置の製造方法は、例えば、接着剤を介して半導体チップ及び配線回路基板を互いに接続すると共に半導体チップ及び配線回路基板のそれぞれの接続部を互いに電気的に接続して半導体装置を得る工程、又は、接着剤を介して複数の半導体チップを互いに接続すると共に複数の半導体チップのそれぞれの接続部を互いに電気的に接続して半導体装置を得る工程を備える。
(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樹脂(三菱ケミカル株式会社製、商品名「EP1032H60」、以下「EP1032」という。)
・ナフタレン骨格含有エポキシ樹脂(DIC株式会社製、商品名「HP4032D」)
・ビスフェノールF型液状エポキシ樹脂(三菱ケミカル株式会社製、商品名「YL983U」、以下「YL983」という。)
・柔軟性エポキシ樹脂(三菱ケミカル株式会社製、商品名「YL7175」、以下「YL7175」という。)
・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」、以下「2MAOK」という。)
・アクリル樹脂(株式会社クラレ製、商品名「クラリティLA4285」、Mw/Mn=1.28、重量平均分子量Mw:80000)
無機フィラー
・エポキシ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「50nmSE-AH1」、平均粒径:約50nm、以下「SEナノシリカ」という。)
・無機シリカフィラー(株式会社アドマテックス製、商品名「SE2050」、平均粒径:0.5μm、以下「SE2050」という。)
・無機シリカフィラー(株式会社アドマテックス製、商品名「SE2050SEJ」、平均粒径:0.5μm、以下「SE2050SEJ」という。)
・グルタル酸(シグマアルドリッチジャパン合同会社製、融点:約97℃)
(実施例1)
エポキシ樹脂11.25g(「EP1032」を6.8g、「HP4032D」を0.75g、「YL983」を1.5g、「YL7175」を2.2g)、硬化剤「2MAOK」0.6g、グルタル酸0.45g、無機フィラー「SEナノシリカ」を35.3g、アクリル樹脂「LA4285」2.0g、及び、シクロヘキサノン(樹脂ワニス中の固形分量が47質量%になる量)を仕込み、直径1.0mmのビーズを固形分と同質量加え、ビーズミル(フリッチュ・ジャパン株式会社製、遊星型微粉砕機P-7)で30分撹拌した。その後、撹拌に用いたビーズをろ過によって除去し、樹脂ワニスを得た。
エポキシ樹脂「HP4032D」を1.5gに増やし、エポキシ樹脂「YL983」を0.75gに減らしたこと以外は、実施例1と同様にして、フィルム状接着剤を作製した。
エポキシ樹脂「YL7175」及び「HP4032D」を配合せず、無機シリカフィラー(株式会社アドマテックス製、商品名「SE2050」、平均粒径:0.5μm)を2.3g加えたこと以外は、実施例1と同様にして、フィルム状接着剤を作製した。
無機シリカフィラー(株式会社アドマテックス製、商品名「SE2050SEJ」、平均粒径:0.5μm)を3.3g加え、「SEナノシリカ」を27.9gに減らし、「LA4285」を0.5gに減らしたこと以外は、実施例1と同様にして、フィルム状接着剤を作製した。
以下、実施例及び比較例で得られたフィルム状接着剤の評価方法を示す。
作製したフィルム状接着剤を卓上ラミネータ(株式会社ミラーコーポレーション製、商品名「ホットドッグGK-13DX」)にて、総厚が0.4mm(400μm)になるまで複数枚ラミネート(積層)し、縦7.3mm、横7.3mmのサイズに切り抜き測定サンプルを得た。
得られた測定サンプルについて、ずり粘度測定装置(ティー・エイ・インスツルメント・ジャパン株式会社製、商品名「ARES」)にて温度120℃の一定条件で周波数を1Hzから70Hzまで0.1Hz毎秒で連続的に変化させた際の粘度を測定し、7Hz時の粘度値を70Hz時の粘度値で割った値をチキソトロピー値とした。
作製したフィルム状接着剤を切り抜き(縦7.3mm、横7.3mm、厚み0.045mm)、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、厚み0.15mm、バンプ高さ:銅ピラー+はんだの合計約45μm、バンプ数328、ピッチ80μm)上に貼付した。次に、フィルム状接着剤を貼付したはんだバンプ付き半導体チップを、ガラスエポキシ基板(ガラスエポキシ基材厚さ:420μm、銅配線厚さ:9μm)にフリップチップボンダーFCB3(パナソニック株式会社製)で実装し(実装条件:圧着ヘッド温度350℃/5秒/0.5MPa)、図4と同様の半導体装置を得た。ステージ温度は80℃とした。
上記の(3)半導体装置の製造方法で得た半導体装置を上側チップの上方からマイクロスコープ(株式会社キーエンス製)にて観察し、チップ端部からの樹脂のはみ出し幅を測定した。はみ出し幅は、チップの1辺の中央からの樹脂のはみ出し幅W1(単位:μm)と、当該1辺の一端(チップの角)から0.2mm中央側の位置からの樹脂のはみ出し幅W2(単位:μm)とを測定し、両者の比(W2/W1)を求めた。なお、W2は、チップの上記1辺の一端から0.2mm中央側の位置からの樹脂のはみ出し幅、及び、他端から0.2mm中央側の位置からの樹脂のはみ出し幅のうち、小さい方の値である。この比(W2/W1)の測定をチップの4辺全てについて行い、その平均値を「カバレッジ性」として求めた。
Claims (8)
- 半導体チップ及び配線回路基板のそれぞれの接続部の電極同士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の電極同士が互いに電気的に接続された半導体装置において、前記接続部の少なくとも一部の封止に用いられる半導体用接着剤であって、
前記半導体用接着剤のチキソトロピー値が、1.0以上、3.1以下であり、
前記チキソトロピー値は、前記半導体用接着剤を厚さ400μmまで積層したサンプルについて、ずり粘度測定装置で温度120℃の一定条件にて周波数を1Hzから70Hzまで連続的に変化させた際の粘度を測定し、7Hz時の粘度値を70Hz時の粘度値で割った値である、半導体用接着剤。 - (a)エポキシ樹脂、(b)硬化剤、及び、(c)重量平均分子量10000以上の高分子量成分を含有する、請求項1に記載の半導体用接着剤。
- さらに(d)フィラーを含有する、請求項2に記載の半導体用接着剤。
- さらに(e)フラックス剤を含有する、請求項2又は3に記載の半導体用接着剤。
- 前記(c)重量平均分子量10000以上の高分子量成分の多分散度Mw/Mnが3以下である、請求項2~4のいずれか一項に記載の半導体用接着剤。
- 前記半導体用接着剤に含有される材料の一部もしくは全てが、シクロヘキサノンに可溶である、請求項2~5のいずれか一項に記載の半導体用接着剤。
- フィルム状である、請求項1~6のいずれか一項に記載の半導体用接着剤。
- 請求項1~7のいずれか一項に記載の半導体用接着剤を用い、接続装置により前記半導体用接着剤を介して半導体チップ及び配線回路基板の位置合わせを行い、互いに接続すると共に半導体チップ及び配線回路基板のそれぞれの接続部の電極同士を互いに電気的に接続し、前記接続部の少なくとも一部を前記半導体用接着剤で封止する工程、又は、接続装置により前記半導体用接着剤を介して複数の半導体チップの位置合わせを行い、互いに接続すると共に複数の半導体チップのそれぞれの接続部の電極同士を互いに電気的に接続し、前記接続部の少なくとも一部を前記半導体用接着剤で封止する工程を備える、半導体装置の製造方法。
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