CN115298280A - Adhesive for semiconductor, semiconductor device and method for manufacturing the same - Google Patents

Adhesive for semiconductor, semiconductor device and method for manufacturing the same Download PDF

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Publication number
CN115298280A
CN115298280A CN202180021009.9A CN202180021009A CN115298280A CN 115298280 A CN115298280 A CN 115298280A CN 202180021009 A CN202180021009 A CN 202180021009A CN 115298280 A CN115298280 A CN 115298280A
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China
Prior art keywords
semiconductor
adhesive
mass
connection
inorganic filler
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CN202180021009.9A
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Chinese (zh)
Inventor
大久保健实
黑田孝博
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Resonac Holdings Corp
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Showa Denko KK
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Publication of CN115298280A publication Critical patent/CN115298280A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/28Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means 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
    • H01L2224/10Bump connectors; Manufacturing methods related thereto
    • H01L2224/15Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161Disposition
    • H01L2224/16135Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/16145Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means 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
    • H01L2224/732Location after the connecting process
    • H01L2224/73201Location after the connecting process on the same surface
    • H01L2224/73203Bump and layer connectors
    • H01L2224/73204Bump and layer connectors the bump connector being embedded into the layer connector

Abstract

An adhesive for a semiconductor, which is used for sealing a connection portion in a semiconductor device having a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other, wherein the adhesive for a semiconductor contains a curable resin component, a flux and an inorganic filler, the content of the inorganic filler is 60 to 95% by mass based on the total amount of the adhesive for a semiconductor, and the thermal conductivity of the adhesive for a semiconductor after curing is 1.5W/mK or more.

Description

Adhesive for semiconductor, semiconductor device and method for manufacturing the same
Technical Field
The present invention relates to an adhesive for a semiconductor, a semiconductor device and a method for manufacturing the same.
Background
Conventionally, a wire bonding method using a fine metal wire such as a gold wire (wire) has been widely used for connecting a semiconductor chip and a substrate, but in order to meet the requirements for high functionality, high integration, high speed, and the like of a semiconductor device, a flip chip connection method (FC connection method) has been widely used in which a conductive protrusion called a bump is formed on a semiconductor chip or a substrate and a direct connection is made between the semiconductor chip and the substrate.
As the flip chip connection method, a method of bonding metals using solder, tin, gold, silver, copper, or the like, a method of bonding metals by applying ultrasonic vibration, a method of maintaining mechanical contact by a contraction force of resin, or the like are known, but from the viewpoint of reliability of a connection portion, a method of bonding metals using solder, tin, gold, silver, copper, or the like is generally employed.
For example, among connections between a semiconductor Chip and a substrate, a Chip On Board (COB) type connection method widely used in BGA (Ball Grid Array), CSP (Chip Size Package), and the like is also a flip Chip connection method. The flip Chip connection method is also widely used for a COC (Chip On Chip) type connection method in which bumps or wires are formed On semiconductor chips and the semiconductor chips are connected to each other (for example, refer to patent document 1 below).
Among the packages strongly required to be further miniaturized, thinned and highly functional, chip stack packages, POPs (Package On packages), TSVs (Through-Silicon vias), and the like, in which the above connection systems are laminated and multilayered, have also begun to be widely used. Since the package can be reduced by disposing the semiconductor wiring substrate in a solid shape instead of a flat shape, these techniques are widely used, and are effective for improving the performance of the semiconductor, reducing noise, reducing the mounting area, and saving power.
Prior art documents
Patent document
Patent document 1: japanese patent laid-open No. 2008-294382
Disclosure of Invention
Technical problem to be solved by the invention
In the flip chip connection method, flip chip connection may be performed with an adhesive for a semiconductor in order to protect metal bonding of the connection portion.
In recent years, flip chip packages have been developed to have higher functions and higher integration, but with the higher functions and higher integration, the pitch between wirings has become narrower, and the amount of heat generated from the package has increased. When heat is accumulated in the package, the semiconductor chip becomes high in temperature, and a failure may occur. Therefore, the adhesive for semiconductor is required to have more excellent heat dissipation than ever before.
Accordingly, an object of the present invention is to provide an adhesive for a semiconductor having excellent heat dissipation properties. It is another object of the present invention to provide a semiconductor device using the adhesive for a semiconductor and a method for manufacturing the semiconductor device.
Means for solving the technical problems
An aspect of the present invention provides an adhesive for a semiconductor, which is used for sealing a connection portion in a semiconductor device including a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other, wherein the adhesive for a semiconductor contains a curable resin component, a flux, and an inorganic filler, the content of the inorganic filler is 60 to 95% by mass based on the total amount of the adhesive for a semiconductor, and the thermal conductivity of the adhesive for a semiconductor after curing is 1.5W/mK or more.
The inorganic filler may contain polyhedral aluminum oxide.
The inorganic filler may contain at least one selected from the group consisting of silicon carbide, boron nitride, diamond, silica, and aluminum nitride.
The inorganic filler may have peaks in the respective ranges of 0.1 to 4.5 μm and 5 to 20 μm in the volume-based particle size distribution.
The binder for semiconductor can be used as an inorganic filler and can be prepared with a volume-based average particle diameter r 1 Polyhedral alumina of 5 to 20 mu m and volume-based average particle diameter r 2 0.1 to 4.5 mu m polyhedral aluminum oxide.
The above average particle diameter r 1 With the above average particle diameter r 2 The difference (r) between 1 -r 2 ) May be 4 to 10 μm.
The thermal conductivity of the adhesive for a semiconductor after curing may be 3.0W/mK or more.
The flux may be a carboxylic acid.
The curable resin component may contain a thermosetting resin, a curing agent, and a thermoplastic resin.
Another aspect of the present invention provides a method of manufacturing a semiconductor device including a connection structure in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, the method including: and sealing at least a part of the connection portion with the adhesive for semiconductor.
Another aspect of the present invention provides a semiconductor device including: a connection structure in which respective connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other and/or a connection structure in which respective connection portions of the plurality of semiconductor chips are electrically connected to each other; and a sealing material for sealing at least a part of the connection portion, the sealing material containing a cured product of the adhesive for a semiconductor.
Effects of the invention
According to the present invention, an adhesive for a semiconductor excellent in heat dissipation can be provided. Further, the present invention can provide a semiconductor device using such an adhesive for a semiconductor and a method for manufacturing the same.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device according to the present invention.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device according to the present invention.
Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device according to the present invention.
Fig. 4 is a schematic cross-sectional view showing an example of the method for manufacturing the semiconductor device shown in fig. 3.
Fig. 5 is a schematic cross-sectional view showing another embodiment of the semiconductor device according to the present invention.
Detailed Description
Hereinafter, a mode for carrying out the present invention will be described in detail with reference to the drawings according to circumstances. However, the present invention is not limited to the following embodiments. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acrylate" means acrylate or methacrylate corresponding thereto. "a or B" may include either one of a and B, or both of them.
In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the minimum value and the maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of a numerical range in one stage may be replaced with the upper limit or the lower limit of a numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.
< adhesive for semiconductor >
The adhesive for a semiconductor according to the present embodiment is an adhesive for a semiconductor used for sealing a connection portion in a semiconductor device having a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other, and contains a curable resin component, a flux and an inorganic filler, wherein the content of the inorganic filler is 60 to 95 mass% based on the total amount of the adhesive for a semiconductor, and the thermal conductivity of the adhesive for a semiconductor after curing is 1.5W/mK or more.
(curable resin component)
The curable resin component may contain (a) a thermosetting resin, (b) a curing agent, and (c) a thermoplastic resin.
((a) thermosetting resin)
Examples of the thermosetting resin include epoxy resin, urea resin, melamine resin, and phenol resin. The thermosetting resin may be an epoxy resin from the viewpoint of good curability and excellent adhesion. The thermosetting resin can be used singly or in combination of two or more.
Examples of the epoxy resin include epoxy resins having 2 or more epoxy groups in a molecule, and examples thereof include bisphenol a type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, and various polyfunctional epoxy resins. These epoxy resins can be used singly or in combination of two or more.
The content of the epoxy resin may be 40 parts by mass or more or 50 parts by mass or more with respect to 100 parts by mass of the curing agent resin component. The content of the epoxy resin may be 90 parts by mass or less or 80 parts by mass or less with respect to 100 parts by mass of the curing agent resin component.
The content of the epoxy resin may be 10 parts by mass or more or 20 parts by mass or more with respect to 100 parts by mass of the adhesive for a semiconductor. The content of the epoxy resin may be 50 parts by mass or less or 40 parts by mass or less with respect to 100 parts by mass of the adhesive for a semiconductor. The content of the epoxy resin may be 10 to 50 parts by mass with respect to 100 parts by mass of the adhesive for semiconductors.
((b) curing agent)
Examples of the curing agent include phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, and phosphine curing agents. When the curing agent contains a phenolic hydroxyl group, an acid anhydride, an amine, or an imidazole, flux activity for suppressing the generation of an oxide film on a connecting portion is easily exhibited, and connection reliability and insulation reliability can be easily improved.
Examples of the phenolic resin curing agent include curing agents having 2 or more phenolic hydroxyl groups in the molecule, and phenol novolacs, cresol novolacs, phenol aralkyl resins, cresol naphthol formaldehyde polycondensates, triphenylmethane type polyfunctional phenols, various polyfunctional phenol resins, and the like can be used. The phenolic resin curing agent may be used singly or in combination of two or more.
When the curable resin component contains an epoxy resin, the equivalent ratio (molar ratio of phenolic hydroxyl groups to epoxy groups) of the phenolic resin curing agent to the epoxy resin may be 0.3 to 1.5, 0.4 to 1.0, or 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalence ratio is 0.3 or more, curability tends to be improved and adhesive force tends to be improved, and when the equivalence ratio is 1.5 or less, unreacted phenolic hydroxyl groups tend not to remain excessively, water absorption is suppressed to be low, and insulation reliability tends to be further improved.
Examples of the acid anhydride curing agent include methylcyclohexane tetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bistrimellitic anhydride ester. The acid anhydride curing agent may be used singly or in combination of two or more.
When the curable resin component contains an epoxy resin, the equivalent ratio of the acid anhydride-based curing agent to the epoxy resin (acid anhydride group/epoxy group, molar ratio) may be 0.3 to 1.5, 0.4 to 1.0, or 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesive force tends to be improved, and when the equivalent ratio is 1.5 or less, unreacted acid anhydride does not excessively remain, water absorption is suppressed to be low, and insulation reliability tends to be further improved.
Examples of the amine-based curing agent include dicyanodiamine.
When the curable resin component contains an epoxy resin, the equivalent ratio (amine/epoxy group molar ratio) of the amine-based curing agent to the epoxy resin may be 0.3 to 1.5, 0.4 to 1.0, or 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesion tends to be improved, and when it is 1.5 or less, unreacted amine tends not to remain excessively, and insulation reliability tends to be further improved.
Examples of the imidazole-based curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, and epoxy resin adduct. Among them, from the viewpoint of more excellent curability, storage stability and connection reliability, the imidazole curing agent may be 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' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole. The imidazole-based curing agent may be used singly or in combination of two or more. These may be used as a latent curing agent for microencapsulation.
The content of the imidazole curing agent may be 0.1 to 20 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.5 to 5 parts by mass with respect to 100 parts by mass of the curable resin component. When the content of the imidazole-based curing agent is 0.1 parts by mass or more, curability tends to be improved, and when it is 20 parts by mass or less, the adhesive composition tends not to be cured before the metal bond is formed, and poor connection tends to be less likely to occur.
Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrakis (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate.
The content of the phosphine-based curing agent may be 0.1 to 10 parts by mass or 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin component. When 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 not cured before metal bonding is formed, and poor connection tends to be less likely to occur.
The phenolic resin curing agent, the acid anhydride curing agent and the amine curing agent may be used singly or in combination of two or more. The imidazole-based curing agent and the phosphine-based curing agent may be used alone or in combination with a phenol resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent.
As the curing agent, from the viewpoint of excellent curability, a phenol resin curing agent and an imidazole curing agent may be used together, an acid anhydride curing agent and an imidazole curing agent may be used together, an amine curing agent and an imidazole curing agent may be used together, or an imidazole curing agent may be used alone. Since productivity is improved when the connection is made in a short time, an imidazole-based curing agent having excellent rapid curability can be used alone. In this case, since volatile components such as low-molecular components can be suppressed during curing in a short time, generation of voids can be easily suppressed.
The content of the curing agent may be 0.1 to 20 parts by mass or 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin component.
((c) thermoplastic resin)
Examples of the thermoplastic resin include phenoxy resins, polyimide resins, polyamide resins, polycarbodiimide resins, cyanate resins, (meth) acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, urethane resins, acrylate rubbers, and the like. The thermoplastic resin may be a phenoxy resin, a polyimide resin, (meth) acrylic resin, an acrylate rubber, a cyanate ester resin, a polycarbodiimide resin, or the like, and may be a phenoxy resin, a polyimide resin, (meth) acrylic resin, or an acrylate rubber, from the viewpoint of excellent heat resistance and film formability. The thermoplastic resin can be used singly or in combination of two or more.
Examples of the phenoxy resin include ZX1356-2 and FX-293 manufactured by NIPPON STEEL Chemical & Material Co., ltd. As the urethane resin, for example, T-8175N manufactured by DIC Covestro Polymer Ltd. which is polyurethane can be used. As the (meth) acrylic resin, for example, an acrylic block copolymer, which is a block copolymer of at least one compound of (meth) acrylate compounds such as (meth) acrylic acid, (meth) acrylate such as methyl (meth) acrylate, and the like, can be used. As the acrylic block copolymer, for example, LA4285, LA2330, and LA2140 (all manufactured by KURARAY co., LTD) which are block copolymers of methyl methacrylate and butyl acrylate can be used. From the viewpoint of further excellent heat dissipation properties, the thermoplastic resin may be a phenoxy resin having a structure (structure with a large number of aromatic rings) in which a crystal structure is easily adopted.
The glass transition temperature (Tg) of the thermoplastic resin may be 120 ℃ or lower, 100 ℃ or lower, or 85 ℃ or lower, from the viewpoint of excellent adhesiveness of the adhesive for a semiconductor to a substrate or a chip. Since the adhesive for a semiconductor contains a thermoplastic resin having a Tg of 120 ℃ or less, the adhesive can suppress a curing reaction, and therefore, the adhesive is easily embedded in bumps formed on a semiconductor chip, electrodes formed on a substrate, a wiring pattern, and other irregularities, and therefore, air bubbles are less likely to remain, and the generation of voids tends to be easily suppressed. Further, since the adhesive for a semiconductor contains a thermoplastic resin having a Tg of room temperature (25 ℃) or higher, the adhesive for a semiconductor can be easily formed into a film or a film.
In the present specification, tg of a thermoplastic resin means that the Tg is measured using differential scanning calorimetry (DSC, model DSC-7 manufactured by PerkinElmer co., ltd.) under conditions of a sample amount of 10mg, a temperature increase rate of 10 ℃/min, a measurement atmosphere: tg when measured under air conditions.
The weight average molecular weight of the thermoplastic resin may be 10000 or more, 30000 or more, 40000 or more, 50000 or more, from the viewpoint of excellent film formability of the adhesive for semiconductors. The weight average molecular weight of the thermoplastic resin may be 1000000 or less or 500000 or less from the viewpoint of excellent film processability of the adhesive for semiconductors.
In the present specification, the weight average molecular weight means a weight average molecular weight when measured in terms of polystyrene using high-speed liquid chromatography (C-R4A manufactured by Shimadzu Corporation).
When the curable resin component contains an epoxy resin and a thermoplastic resin, the content of the epoxy resin may be 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, and may be 500 parts by mass or less, 400 parts by mass or less, or 300 parts by mass or less, with respect to 100 parts by mass of the thermoplastic resin. The content of the epoxy resin may be 1 to 500 parts by mass, 5 to 400 parts by mass, or 10 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the content of the epoxy resin is within these ranges, the adhesive for a semiconductor has sufficient curability and excellent adhesion, and the adhesive for a semiconductor can be easily formed into a film or film shape.
The content of the thermoplastic resin may be 0.1 part by mass or more, 1 part by mass or more, or 10 parts by mass or more, and may be 50 parts by mass or less or 40 parts by mass or less, with respect to 100 parts by mass of the curable resin component. The content of the thermoplastic resin may be 0.1 to 50 parts by mass, 1 to 50 parts by mass, or 10 to 40 parts by mass with respect to 100 parts by mass of the curable resin component.
The content of the curable resin component may be 10 mass% or more or 30 mass% or more, and may be 70 mass% or less or 50 mass% or less, based on the total amount of the adhesive for a semiconductor. The content of the curable resin component may be 10 to 70% by mass, 10 to 50% by mass, or 30 to 50% by mass, based on the total amount of the adhesive for a semiconductor.
(fluxing agent)
The adhesive for a semiconductor according to the present embodiment may further contain a flux (i.e., a flux activator that exhibits flux activity (activity for removing oxides, impurities, and the like)). Examples of the flux include nitrogen-containing compounds (imidazoles, amines, and the like), carboxylic acids, phenols, and alcohols having an unshared electron pair.
The flux may contain an organic acid that reacts with the epoxy resin, from the viewpoint of exhibiting a stronger flux activity than alcohols and easily improving the connectivity.
When the curable resin component contains an epoxy resin, the curable resin component reacts with the epoxy resin and does not exist in a free state in a cured product of the adhesive for a semiconductor, and therefore, the reduction in insulation reliability can be prevented.
Examples of the carboxylic acid include: aliphatic saturated carboxylic acids such as ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid; aliphatic unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, and the like; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; aromatic carboxylic acids such as benzoic acid (benzoic acid), phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, pentanecarboxylic acid, and benzoic acid (mesic acid); maleic acid and fumaric acid. Examples of the carboxylic acid having a hydroxyl group include lactic acid, malic acid, citric acid, salicylic acid, and the like.
The carboxylic acid may be a dicarboxylic acid. Since dicarboxylic acids are relatively less volatile than monocarboxylic acids, voids tend to be suppressed. Further, since dicarboxylic acids are less likely to react at low temperatures (temperatures below the junction, e.g., 100 ℃ or lower) in film formation, lamination, preheating, etc., they tend not to have too high a viscosity, and thus can suppress poor connection.
The carboxylic acid may be a carboxylic acid having one or more alkyl groups at positions 2 or 3 to the carboxyl group. Examples of the carboxylic acid having such an alkyl group include 2-methylglutaric acid, 3-methylglutaric acid and the like.
The content of the flux may be 0.5 parts by mass or more, 1 part by mass or more, or 1.5 parts by mass or more with respect to 100 parts by mass of the adhesive for a semiconductor. The content of the flux may be 10 parts by mass or less or 5 parts by mass or less with respect to 100 parts by mass of the adhesive for a semiconductor. The content of the flux may be 0.5 to 10 parts by mass or 0.5 to 5 parts by mass with respect to 100 parts by mass of the adhesive for a semiconductor.
(inorganic Filler)
The adhesive for semiconductors of the present embodiment contains an inorganic filler. The content of the inorganic filler is 60 to 95 mass% based on the total amount of the adhesive for semiconductors. When the content of the inorganic filler is within the above range, the adhesive for a semiconductor can be provided with excellent heat dissipation properties.
Examples of the inorganic filler include alumina (Al) 2 O 3 ) Magnesium oxide, silicon carbide, boron nitride, diamond, aluminum nitride. The inorganic filler may contain at least one selected from the group consisting of alumina, silicon carbide, boron nitride, diamond, and aluminum nitride, from the viewpoint of the thermal conductivity of the binder for a semiconductor.
When the inorganic filler is particles containing alumina (hereinafter, also referred to as "alumina filler"), the alumina may be α -alumina. The alumina of the alumina filler may have a purity of 99.0 mass% or more, 99.5 mass% or more, or 99.9 mass% or more, from the viewpoint of excellent heat dissipation of the adhesive for a semiconductor. The purity of the alumina filler may be such that the alumina filler is substantially composed of alumina (100 mass% of the alumina filler is substantially alumina).
The shape of the alumina filler is not particularly limited, and examples thereof include a spherical shape, a substantially spherical shape, a polyhedral shape, a needle shape, and a plate shape. Among them, the adhesive for a semiconductor may be spherical, polyhedral or polyhedral in view of excellent heat dissipation properties. In the present specification, the term "polyhedron" refers to a solid body having a plurality of planes as a constituent of a surface. A plurality of planes may be present and may intersect each other via a curved surface (may be rounded at corners). The polyhedron may have, for example, planes of 4 to 100 as a constituent of the surface.
The reason why the heat dissipation property of the adhesive for semiconductors is excellent is not necessarily clear by using polyhedral alumina as the alumina filler, but the present inventors believe that the heat transfer is improved by increasing the heat transfer area because the fillers are in surface contact with each other by the polyhedral alumina filler.
The average particle diameter of the inorganic filler may be 20 μm or less, 15 μm or less, or 10 μm or less from the viewpoint of improving film formability when the adhesive for a semiconductor is formed into a film shape. The average particle diameter of the inorganic filler may be 0.1 μm or more, 0.5 μm or more, or 1 μm or more from the viewpoint of dispersibility of the inorganic filler.
In the present specification, the term "average particle diameter" means a particle diameter at a point corresponding to 50% by volume when a cumulative frequency distribution curve based on particle diameters is obtained with the total volume of particles as 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.
The alumina filler may be an alumina filler having an alumina surface treated from the viewpoint of further improving visibility, dispersibility, and adhesion. Examples of the surface treatment agent include a glycidyl (epoxy) compound, an amine compound, a phenyl compound, a phenylamino compound, a (meth) acrylic compound (for example, a compound having a structure represented by the following general formula (1)), a vinyl compound having a structure represented by the following general formula (2), and the like.
Figure BDA0003844317000000101
[R 11 Represents a hydrogen atom or an alkyl group, R 12 Represents an alkylene group.]
As the filler surface-treated with the compound having the structure represented by the formula (1), R is exemplified 11 Acrylic surface-treated fillers being hydrogen atoms, R 11 Methacrylic surface-treating fillers, R, being methyl 11 Ethyl acrylic acid surface treatment fillers which are ethyl groups, and the like. From the viewpoint of reactivity with the resin contained in the adhesive for semiconductor and the surface of the semiconductor substrate, and bond formation, R 11 May be a hydrogen atom or a methyl group as a substituent having a small volume. The surface-treated filler may be an acrylic surface-treated filler or a methacrylic surface-treated filler. R is 12 The alkylene group (b) is not particularly limited, but may be a group having a high weight average molecular weight from the viewpoint of reduction of volatile components.
Figure BDA0003844317000000111
[R 21 、R 22 And R 23 Each independently represents a hydrogen atom or an alkyl group, R 24 Represents an alkylene group.]
From the viewpoint of not lowering reactivity, R 21 、R 22 And R 23 May be a substituent having a small volume. And may be a substituent in which reactivity of the vinyl group in formula (2) is improved. R 24 There is no particular limitation, but from the viewpoint of non-volatility and reduction of voids, it may be a group having a high weight average molecular weight. And, R 21 、R 22 、R 23 And R 24 And may be selected according to the ease of surface treatment. For example, R 21 、R 22 And R 23 The hydrogen atom and the methyl group may be used.
The surface treatment agent may be a silane compound such as epoxy silane, amino silane, (meth) acrylic silane, or vinyl silane, because of the ease of surface treatment. In addition, the alumina filler may be an alumina filler whose surface is silane-treated, from the viewpoint that the adhesive for a semiconductor is more excellent in transparency. The surface treatment agent may be a glycidyl silane compound, a phenylamino silane compound, (meth) acrylic acid, or a vinyl silane compound, from the viewpoint of excellent dispersibility, fluidity, and adhesive force. The surface treatment agent may be a vinyl, phenylamino or (meth) acrylic silane compound, from the viewpoint of excellent storage stability.
The inorganic filler may be used singly or in combination of two or more different kinds. The inorganic filler to be used simultaneously may be, for example, two or more different kinds of inorganic fillers such as an alumina filler and silicon carbide. The inorganic filler used at the same time may be two or more kinds of the same kind of inorganic fillers different in shape, average particle diameter, surface treatment, and the like.
The inorganic filler to be used simultaneously may be two or more kinds of the same kind of inorganic filler, two or more kinds of alumina filler, two or more kinds of polyhedral alumina, or two or more kinds of polyhedral alumina having different average particle diameters, from the viewpoint of more excellent heat dissipation properties.
In the case where two or more kinds of inorganic fillers are used, the inorganic filler may have a plurality of peaks in a volume-based particle size distribution, and may have peaks in the ranges of 0.1 to 4.5 μm and 5 to 20 μm, from the viewpoint of more excellent heat dissipation properties. In the present specification, the term "peak" refers to a maximum value of the number frequency in a volume-based particle size distribution.
One peak (first peak) among the plurality of peaks may be 5 to 15 μm, 5 to 10 μm, or 5 to 8 μm from the viewpoint of more excellent heat dissipation properties. One peak (second peak) among the plurality of peaks may be 0.1 to 3.0 μm, 0.1 to 2.0 μm, or 0.1 to 1.5 μm from the viewpoint of more excellent heat dissipation properties.
From the viewpoint of more excellent heat dissipation, the difference between the peak positions of the first peak and the second peak may be 4 μm or more or 5 μm or more, and may be 10 μm or less, 8 μm or less or 7 μm or less. The difference between the peak positions of the first peak and the second peak may be 4 to 10 μm, 4 to 8 μm, or 5 to 7 μm.
The inorganic filler having a plurality of peaks in the volume-based particle size distribution can be obtained by simultaneously using two or more types of inorganic fillers having different mode diameters or average particle sizes. The inorganic filler to be used simultaneously may be, for example, an inorganic filler having a mode diameter or an average particle diameter of 5 to 20 μm and an inorganic filler having a mode diameter or an average particle diameter of 0.1 to 4.5. Mu.m.
From the viewpoint of more excellent heat dissipation properties, the adhesive for semiconductors may be prepared with a first inorganic filler having a mode diameter or average particle diameter of 5 to 20 μm and a second inorganic filler having a mode diameter or average particle diameter of 0.1 to 4.5 μm. The first inorganic filler may have a mode diameter or an average particle diameter of 5 to 15 μm, 5 to 10 μm, or 5 to 8 μm. The second inorganic filler may have a mode diameter or an average particle diameter of 0.1 to 3.0. Mu.m, 0.1 to 2.0. Mu.m, or 0.1 to 1.5. Mu.m.
The binder for semiconductor may be formulated to have an average particle diameter r from the viewpoint of more excellent heat dissipation 1 A first polyhedral aluminum oxide of 5 to 20 mu m and an average particle diameter r 2 A second polyhedral aluminum oxide of 0.1 to 4.5 μm. Average particle diameter r of first polyhedral alumina 1 May be 5 to 15 μm, 5 to 10 μm or 5 to 8 μm. Average particle diameter r of second polyhedral aluminum oxide 2 May be 0.1 to 3.0. Mu.m, 0.1 to 2.0. Mu.m, or 0.1 to 1.5. Mu.m.
The average particle diameter r of the first polyhedral alumina from the viewpoint of more excellent heat dissipation properties 1 And the average particle diameter r of the second polyhedral aluminum oxide 2 Difference of difference (r) 1 -r 2 ) May be 4 to 10 μm, 4 to 8 μm or 5 to 7 μm.
The amount of the first polyhedral aluminum oxide and the second polyhedral aluminum oxide to be blended may be 10 to 70 parts by mass, 10 to 50 parts by mass, or 10 to 30 parts by mass per 100 parts by mass of the first polyhedral aluminum oxide.
From the viewpoint of more excellent heat dissipation properties, the content of the first polyhedral aluminum oxide in the binder for a semiconductor may be 60 mass% or more or 70 mass% or more, and may be 90 mass% or less or 85 mass% or less, based on the total amount of the binder for a semiconductor. The content of the first polyhedral aluminum oxide in the adhesive for a semiconductor may be 60 to 90% by mass or 70 to 85% by mass, based on the total amount of the adhesive for a semiconductor.
From the viewpoint of more excellent heat dissipation properties, the content of the second polyhedral aluminum oxide in the binder for a semiconductor may be 10 mass% or more or 15 mass% or more, and may be 30 mass% or less or 20 mass% or less, based on the total amount of the binder for a semiconductor. The content of the second polyhedral aluminum oxide in the adhesive for a semiconductor may be 10 to 30% by mass or 15 to 20% by mass, based on the total amount of the adhesive for a semiconductor.
From the viewpoint of more excellent heat dissipation properties, the content of the inorganic filler may be 75 mass% or more or 85 mass% or more based on the total amount of the binder for a semiconductor. In addition, in the case where the inorganic filler is two or more kinds of inorganic fillers, the content of the inorganic filler means the total amount of all the inorganic fillers.
When the inorganic filler is an alumina filler, the content of the alumina filler may be 75 mass% or more or 85 mass% or more based on the total amount of the binder for a semiconductor, from the viewpoint of more excellent heat dissipation. In addition, in the case where the inorganic filler is two or more kinds of alumina fillers, the content of the alumina filler means the total amount of all the alumina fillers.
When the inorganic filler is a mixture of two or more alumina fillers having different average particle diameters or mode diameters, the content of the alumina filler having the largest average particle diameter or mode diameter may be 60 to 90 mass% or 70 to 85 mass% based on the total amount of the binder for a semiconductor, from the viewpoint of more excellent heat dissipation.
(others)
The adhesive for a semiconductor of the present embodiment may further contain additives such as an organic filler (resin filler), an antioxidant, a silane coupling agent (excluding a compound conforming to a flux), a titanium coupling agent, and a leveling agent. These additives can be used singly or in combination of two or more. The content of each additive may be appropriately adjusted so that the effect of the additive is exhibited.
As the material of the organic filler, polyurethane, polyimide, or the like can be used. The resin filler is effective in improving film formability because it can impart flexibility at high temperatures such as 260 ℃ as compared with an inorganic filler.
(thermal conductivity)
The adhesive for a semiconductor according to the present embodiment has a thermal conductivity of 1.5W/mK or more after curing. The adhesive for a semiconductor, which has a thermal conductivity of 1.5W/mK or more after curing, can be provided with excellent heat dissipation properties.
From the viewpoint of more excellent heat dissipation, the thermal conductivity of the adhesive for a semiconductor after curing may be 2.0W/mK or more, 2.5W/mK or more, 3.0W/mK or more, 3.5W/mK or more, or 4.0W/mK or more.
The thermal conductivity of the adhesive for a semiconductor after curing can be calculated by measuring the thermal diffusivity by a laser flash method (Xe-flash method) and multiplying the specific heat and density by the thermal diffusivity, and specifically, the thermal conductivity can be obtained by the method described in the following examples.
The adhesive for a semiconductor can be cured by heating at 240 ℃ for 1 hour, and specifically, a cured adhesive for a semiconductor can be obtained by the method described in the following examples.
The adhesive for a semiconductor of the present embodiment can be formed in a film shape or a film shape. The thickness of the adhesive for a semiconductor (film-like adhesive) in a film form or a film form may be, for example, 100 μm or less, 80 μm or less, or 50 μm or less. The lower limit of the thickness of the film-like adhesive is not particularly limited, and may be 1 μm or more or 5 μm or more.
< method for producing adhesive for semiconductor >
The adhesive for a semiconductor in a film or film form can be obtained by the following method. First, the curable resin component, the flux, the inorganic filler, and other components are added to an organic solvent, and then dissolved or dispersed by stirring, mixing, kneading, or the like to prepare a resin varnish. Then, a resin varnish is applied to the base film subjected to the release treatment by using a knife coater, a roll coater, an applicator, a die coater, a comma coater (comma coater), or the like, and then the organic solvent is reduced by heating, thereby forming an adhesive for a semiconductor on the base film. Alternatively, before the organic solvent is reduced by heating, a resin varnish may be spin-coated on a wafer or the like to form a film, and then the solvent may be dried to form the adhesive for a semiconductor on the wafer.
The base film is not particularly limited as long as it has heat resistance capable of withstanding heating conditions when the organic solvent is volatilized, and examples thereof include a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, and a methylpentene film. The base film is not limited to a single-layer film composed of one of these films, and may be a multilayer film composed of two or more kinds of films.
Specifically, the organic solvent may be heated at 50 to 200 ℃ for 0.1 to 90 minutes as a condition for volatilizing the organic solvent from the resin varnish after coating. The organic solvent may be evaporated to 1.5% or less as long as it does not affect the gap after mounting, viscosity adjustment, and the like.
< semiconductor device >
A semiconductor device manufactured using the adhesive for a semiconductor according to the present embodiment will be described. The semiconductor device according to the present embodiment includes a connection structure in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, and/or a connection structure in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, and a sealing material that seals at least a part of the connection portions, and the sealing material contains a cured product of the adhesive for a semiconductor according to the present embodiment. The connection portion in the semiconductor device may be any of a bump-to-wiring metal bond and a bump-to-bump metal bond. In the semiconductor device according to the present embodiment, for example, flip chip connection in which electrical connection is obtained through an adhesive for a semiconductor can be used.
Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB type connection method of a semiconductor chip and a substrate). As shown in fig. 1 a, the semiconductor device 100 includes a semiconductor chip 10 and a substrate (circuit wiring substrate) 20 facing each other, wires 15 respectively disposed on the surfaces of the semiconductor chip 10 and the substrate 20 facing each other, connection bumps 30 connecting the wires 15 of the semiconductor chip 10 and the substrate 20 to each other, and a sealing material 40 filling a gap between the semiconductor chip 10 and the substrate 20 without a gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by the wires 15 and the connection bumps 30. The wiring 15 and the connection bump 30 are sealed by a sealing material 40 and are isolated from the external environment. The sealing material 40 contains a cured product of the adhesive for a semiconductor according to the present embodiment.
As shown in fig. 1 (b), the semiconductor device 200 includes a semiconductor chip 10 and a substrate 20 facing each other, bumps 32 respectively disposed on the facing surfaces of the semiconductor chip 10 and the substrate 20, and a sealing material 40 filling the gap between the semiconductor chip 10 and the substrate 20 without a gap. The semiconductor chip 10 and the substrate 20 are connected to each other by the opposing bumps 32 and flip chip connected. The bump 32 is sealed by a sealing material 40 and isolated from the external environment.
Fig. 2 is a schematic cross-sectional view showing another embodiment of a semiconductor device (COC type connection method between semiconductor chips). The semiconductor device 300 is similar to the semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wires 15 and connection bumps 30 as shown in fig. 2 (a). The semiconductor device 400 is the same as the semiconductor device 200 except that two semiconductor chips 10 are flip-chip connected by bumps 32 as shown in fig. 2 (b).
The semiconductor chip 10 is not particularly limited, and various semiconductors such as an element semiconductor composed of the same kind of element such as silicon and germanium, and a compound semiconductor such as gallium arsenide and indium phosphide can be used.
The substrate 20 is not particularly limited as long as it is a wired circuit substrate, and a circuit substrate in which unnecessary portions of a metal layer formed on a surface of an insulating substrate mainly composed of glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, polyimide, or the like are removed by etching to form wiring (wiring pattern), a circuit substrate in which wiring (wiring pattern) is formed on a surface of the insulating substrate by metal plating or the like, a circuit substrate in which wiring (wiring pattern) is formed by printing a conductive material on a surface of the insulating substrate, or the like can be used.
The connection portions such as the wiring 15 and the bump 32 contain gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, and tin-copper), nickel, tin, lead, and the like as main components, and may contain a plurality of metals.
A metal layer containing gold, silver, copper, solder (main component such as tin-silver, tin-lead, tin-bismuth, and tin-copper), tin, nickel, or the like as a main component may be formed on the surface of the wiring (wiring pattern). The metal layer may be composed of only a single component or may be composed of a plurality of components. Further, a plurality of metal layers may be stacked. The metal layer may be copper or solder because it is inexpensive and commonly used, but it has an oxide or an impurity, and thus flux activity is required.
The material of the conductive bump called a bump is mainly composed of gold, silver, copper, solder (mainly composed of tin-silver, tin-lead, tin-bismuth, and tin-copper), tin, nickel, or the like, and may be composed of only a single component or a plurality of components. Further, these metals may be stacked. The bumps may also be formed on a semiconductor chip or substrate. The bumps may be copper or solder because they are inexpensive and commonly used, but they have oxides or impurities, and thus require flux activity.
Further, the semiconductor devices (packages) shown in fig. 1 or 2 may be stacked and electrically connected to each other by gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, and tin-copper), tin, nickel, or the like. Since it is inexpensive and generally used, copper or solder can be used for connection, but since it contains an oxide or an impurity, flux activity is required. For example, as seen in the TSV technology, a semiconductor adhesive may be interposed between semiconductor chips to perform flip-chip connection or lamination, and holes may be formed through the semiconductor chips to connect to electrodes on the pattern surface.
Fig. 3 is a schematic cross-sectional view showing another embodiment of a semiconductor device (semiconductor chip stacking Type (TSV)). In the semiconductor device 500 shown in fig. 3, the wirings 15 formed on the interposer (interposer) 50 are connected to the wirings 15 of the semiconductor chip 10 via the connection bumps 30, whereby the semiconductor chip 10 and the interposer 50 are flip-chip connected. The sealing material 40 is filled in the gap between the semiconductor chip 10 and the interposer 50 without a gap. The semiconductor chip 10 is repeatedly stacked on the surface of the semiconductor chip 10 on the side opposite to the interposer 50 via the wiring 15, the connection bump 30, and the sealing material 40. The wirings 15 of the pattern surfaces of the front surface and the back surface of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes penetrating the inside of the semiconductor chip 10. As a material of the through electrode 34, copper, aluminum, or the like can be used.
With such TSV technology, signals can be obtained from the back surface of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 vertically passes through the semiconductor chips 10, the distance between the opposing semiconductor chips 10 or between the semiconductor chip 10 and the interposer 50 can be shortened, and flexible connection can be performed. The adhesive for a semiconductor according to the present embodiment can be applied as a sealing material between the opposing semiconductor chips 10 or between the semiconductor chip 10 and the interposer 50 in the TSV technology.
In addition, in a bump forming method with a high degree of freedom such as the area bump chip technique, the semiconductor chip can be directly mounted on the motherboard without interposing an interposer. The adhesive for a semiconductor according to the present embodiment can also be applied to a case where such a semiconductor chip is directly mounted on a motherboard. The adhesive for a semiconductor according to the present embodiment is also applicable to sealing a gap between substrates when two wiring circuit substrates are stacked.
Fig. 5 is a schematic cross-sectional view showing another embodiment of the semiconductor device (COB type connection method of the semiconductor chip and the substrate). In the semiconductor device 600 shown in fig. 5, a substrate (glass epoxy substrate) 60 having wires (copper wires) 15 and a semiconductor chip 10 having wires (copper pillars (pilars) and post) 15 are connected to each other via a sealing material 40. The wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are electrically connected by a connection bump (solder bump) 30. On the surface of the substrate 60 on which the wiring 15 is formed, a solder resist layer 70 is disposed except for the formation position of the connection bump 30. The semiconductor chip 10 may have a through electrode.
< method for manufacturing semiconductor device >
In the method for manufacturing a semiconductor device according to the present embodiment, the semiconductor device includes a connection structure in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, and the method includes: a step of sealing at least a part of the connection portion using the adhesive for a semiconductor according to the present embodiment.
The above-described steps can be performed by connecting the semiconductor chip and the printed circuit board or the plurality of semiconductor chips to each other using the adhesive for a semiconductor according to the present embodiment. In this case, the method for manufacturing a semiconductor device according to the present embodiment may include, for example: a step of connecting the semiconductor chip and the printed circuit board with each other via an adhesive for semiconductor and electrically connecting the respective connection portions of the semiconductor chip and the printed circuit board, and/or a step of connecting a plurality of semiconductor chips with each other via an adhesive for semiconductor and electrically connecting the respective connection portions of the plurality of semiconductor chips with each other.
In the method for manufacturing a semiconductor device according to the present embodiment, the connection portions can be connected to each other by metal bonding. That is, the connection portions of the semiconductor chips and the wired circuit board may be connected to each other by metal bonding or the connection portions of the semiconductor chips may be connected to each other by metal bonding.
A method for manufacturing a semiconductor device 500 shown in fig. 3 will be described as an example of a method for manufacturing a semiconductor device according to the present embodiment. In the semiconductor device 500, the wirings (copper wirings) 15 formed on the interposer 50 are connected to the wirings (copper pillars (posts) and post) 15 of the semiconductor chip 10 via the connection bumps (solder bumps) 30, and the semiconductor chip 10 and the interposer 50 are flip-chip connected. The sealing material 40 is filled in the gap between the semiconductor chip 10 and the interposer 50 without a gap. The semiconductor chip 10 is repeatedly stacked on the surface of the semiconductor chip 10 on the side opposite to the interposer 50 via the wiring 15, the connection bump 30, and the sealing material 40. The wirings 15 of the pattern surfaces of the front surface and the back surface of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes penetrating the inside of the semiconductor chip 10.
Fig. 4 is a diagram for explaining an example of the method for manufacturing the semiconductor device shown in fig. 3. Fig. 4 (a) shows a step of pressure-bonding a laminated chip having a semiconductor adhesive provided on a main surface of a semiconductor chip to another semiconductor chip with the semiconductor adhesive interposed therebetween. The stacked chip (stacked semiconductor chip) 700 includes a semiconductor chip 10 and a semiconductor adhesive 42 provided on a main surface of the semiconductor chip 10, and the semiconductor chip 10 is provided with a through electrode 34 filled in a hole penetrating the semiconductor chip 10, a wiring 15 arranged on one surface of the semiconductor chip 10, and a connection bump 30 arranged on the wiring 15. The semiconductor adhesive 42 is provided to embed the wiring 15 and the connection bump 30, but may cover at least a part of the surface of the semiconductor chip 10, the wiring 15, and the connection bump 30.
The laminated chip 700 can be produced by applying the semiconductor adhesive 42 to a semiconductor wafer having the wiring 15 and the connection bump 30, or by attaching the semiconductor adhesive 42 in a film form and dicing the semiconductor chip 10. The adhesive for a film-shaped semiconductor can be attached by heat pressing, roll lamination, vacuum lamination, or the like.
The laminated chip 700 and another semiconductor chip can be pressure-bonded, for example, as follows: the connection bumps 30 of the laminated chip 700 are aligned so as to be electrically connected to the through electrodes 34 filled in the holes penetrating the other semiconductor chip 10, and the laminated chip 700 and the semiconductor chip 10 are pressure bonded by using the pressure bonding tool 90 while heating the laminated chip 700 and the semiconductor chip 10 at a temperature equal to or higher than the melting point of the connection bumps 30 (in the case where solder is used for the connection portions, the temperature applied to the solder portions may be 240 ℃. This allows the stacked chip 700 to be connected to the semiconductor chip 10, and the connection portion to be sealed with a cured product of the adhesive for semiconductor.
The connection load depends on the number of bumps, but may be set in consideration of absorption of height variations of the bumps, control of the amount of deformation of the bumps, and the like. The connection time may be short from the viewpoint of improving productivity. The connection time may be a time during which the solder is melted to remove an oxide film, impurities on the surface, and the like, thereby forming a metal bond on the connection portion. The short connection time (crimping time) is a time (for example, a time when solder is used) during which a temperature of 240 ℃ or higher is applied to the connection portion during connection formation (main crimping) and is 10 seconds or less. The connection time may be 5 seconds or less or 3 seconds or less. The same method can be applied to the connection between the interposer 50 having the wiring 15 and the stacked chip 700.
By repeating the above steps, the semiconductor device 500 shown in fig. 4 (b) can be manufactured. The semiconductor device 500 may be manufactured by repeating the steps of aligning and stacking (temporarily fixing) the stacked chip 700 and the semiconductor chip 10 to obtain a temporarily fixed multilayer stack, and then performing a heating process in a reflow furnace to melt the solder bumps and connect the semiconductor chips together. Since the temporary fixation does not significantly require the necessity of forming a metal bond, it is possible to have advantages such as a low load, a short time, and a low temperature, an improvement in productivity, and prevention of deterioration of the connection portion, compared to the above-described main pressure bonding. After the semiconductor chip and the substrate are connected, the adhesive for a semiconductor may be cured by heat treatment in an oven or the like. The heating temperature may be a temperature at which the adhesive for semiconductor sealing is cured and completely cured. The heating temperature and the heating time may be appropriately set.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
< preparation of adhesive for semiconductor >
Compounds used for producing the adhesive for semiconductor are shown below.
(curable resin component)
((a) epoxy resin)
Polyfunctional solid Epoxy resin containing triphenol methane skeleton (manufactured by Japan Epoxy Resins Co. Ltd., product name "EP1032H 60")
Bisphenol F type liquid Epoxy resin (manufactured by Japan Epoxy Resins Co. Ltd., product name "YL 983U")
Flexible Epoxy resin (manufactured by Japan Epoxy Resins Co. Ltd., product name "YL 7175")
((b) curing agent)
2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct (Shikoku Chemicals corporation, product name "2 MAOK-PW")
((c) thermoplastic resin)
Phenoxy resin (NIPPON STEEL Chemical & Material Co., ltd., product name "ZX1356-2", tg: about 71 ℃ C., mw: about 63000)
(inorganic Filler)
Polyhedral alumina 1 (Sumitomo Chemical Co., ltd., AA-04, average particle diameter: 0.41 μm)
Polyhedral alumina 2 (Sumitomo Chemical Co., ltd., AA-07, average particle diameter: 0.83 μm)
Polyhedral alumina 3 (Sumitomo Chemical Co., ltd., AA-1.5, average particle diameter: 1.6 μm)
Polyhedral aluminum oxide 4 (Sumitomo Chemical Co., ltd., AA-3, average particle diameter: 3.7 μm)
Polyhedral alumina 5 (Sumitomo Chemical Co., ltd., AA-5, average particle diameter: 6.6 μm)
Polyhedral aluminum oxide 6 (Sumitomo Chemical Co., ltd., AA-10, average particle diameter: 14.5 μm)
Silicon carbide 1 (TOMOE Engineering Co., ltd., α SiC2500N, average particle diameter: 0.87 μm)
Silicon carbide 2 (TOMOE Engineering Co., ltd.,. Beta.SiC 2500N, average particle diameter: 0.82 μm)
Boron nitride 1 (Momentive, PT132, average particle size: 5.1 μm)
Boron nitride 2 (Momentive, AC6041, average particle size: 5.4 μm)
Boron nitride 3 (Momentive, TECO20191251, average particle size: 4.5 μm)
Diamond (Tomei Diamond, CMM2-4, average particle size: 2.4 μm)
(Filler)
Inorganic silica filler (Admatechs Co., ltd., SE2050, average particle diameter: 500 nm)
(fluxing agent)
Glutaric acid (manufactured by Wako Pure Chemical Corporation, and optical grade, melting point: about 95 ℃ C.)
(example 1)
Thermosetting resin ("EP 1032H60"45 parts by mass, "YL983U"15 parts by mass, "YL7175"5 parts by mass), curing agent 2 parts by mass, inorganic filler (amount shown in table 1, unit: mass% (based on the total amount of the binder for semiconductor)), organic filler 10 parts by mass, and flux 4 parts by mass were added to the organic solvent (cyclohexanone) so that NV (nonvolatile content concentration) became 55% by mass. Then, beads of Φ 1.0mm and beads of Φ 2.0mm, which were equal in mass to the solid content, were added thereto, and the mixture was stirred for 30 minutes by a bead mill (Fritsch Japan Co., ltd., manufactured by Ltd., planetary type micro-pulverizer P-7). Then, 30 parts by mass of a phenoxy resin was added as a thermoplastic resin, and the mixture was stirred again for 30 minutes by a bead mill. The beads used in the stirring were removed by filtration. The varnish thus prepared was applied by a small-size precision coating apparatus (manufactured by Yasui Seiki Inc.) and dried (100 ℃ C./10 minutes) in a clean oven (manufactured by ESPEC CORP.), whereby a film-like adhesive (adhesive for semiconductor) having a thickness of 400 μm was obtained.
(examples 2 to 21, comparative example 1)
A film-like adhesive (adhesive for semiconductor) was obtained in the same manner as in example 1, except that the kind and content of the inorganic filler were changed as shown in tables 1 to 4. Further, the difference between the average particle diameters in tables 3 and 4 was calculated from the absolute value of the difference between the average particle diameters of the inorganic fillers used together.
< evaluation >
(1) Thermal conductivity measurement
The prepared film-like adhesive was cut into pieces of 1cm × 1cm, and cured at 240 ℃ for 1 hour in a clean oven (manufactured by ESPEC corp). Both surfaces of the obtained cured product were blackened by graphite spraying, and the thermal diffusivity in the thickness direction was measured. The thermal diffusivity was measured by a laser flash method (Xe-flash method) (LFA 447 nanoflash, manufactured by NETZSCH corporation). Pulsed light irradiation was performed under the conditions of a pulse width of 0.1 (ms) and an applied voltage of 236V. The measurements were carried out at an atmospheric temperature of 25 ℃. + -. 1 ℃. Next, the specific heat and the density are multiplied by the thermal diffusivity using the following formula (I), thereby obtaining a value of the thermal conductivity. The results are shown in tables 1 to 4.
λ = α × Cp × p
[ in the formula (I), λ represents thermal conductivity (W/mK), α represents thermal diffusivity (m 2/s), cp represents specific heat (J/kg. K), and ρ represents density (g/cm) 3 )。]
Further, the specific heat (J/kg · K) was measured using Differential Scanning Calorimetry (DSC) in the following procedure. The adhesive for a semiconductor was weighed in an aluminum pan, and measured at room temperature (25 ℃) to 60 ℃ at 10 ℃/min using a differential scanning calorimeter (PerkinElmer Japan co., ltd., pyris 1). Sapphire was used as a reference. The known specific heat of sapphire was used to calculate the specific heat of the sample at 25 ℃.
The density (g/cm) was measured at 25 ℃ of water using an electron densitometer (Alfa Mirage co., ltd., SD-200L) 3 )。
Figure BDA0003844317000000221
Figure BDA0003844317000000231
Figure BDA0003844317000000241
[ Table 4]
Figure BDA0003844317000000251
In the examples, it was confirmed that excellent heat dissipation was obtained. In comparative example 1, it was confirmed that sufficient heat dissipation property was not obtained.
Description of the symbols
10-semiconductor chip, 15-wiring, 20, 60-substrate, 30-connection bump, 32-bump, 34-through electrode, 40-sealing material, 42-adhesive for semiconductor, 50-interposer, 70-solder mask, 90-crimping tool, 100, 200, 300, 400, 500, 600-semiconductor device, 700-stacked chip.

Claims (11)

1. An adhesive for semiconductor, which is used for sealing a connection portion in a semiconductor device having a connection structure in which connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which connection portions of a plurality of semiconductor chips are electrically connected to each other,
the adhesive for semiconductor comprises a curable resin component, a flux and an inorganic filler,
the content of the inorganic filler is 60 to 95 mass% based on the total amount of the adhesive for a semiconductor, and the thermal conductivity of the adhesive for a semiconductor after curing is 1.5W/mK or more.
2. The adhesive for semiconductors according to claim 1, wherein,
the inorganic filler contains polyhedral aluminum oxide.
3. The adhesive for semiconductors according to claim 1 or 2, wherein,
the inorganic filler contains at least one selected from the group consisting of silicon carbide, boron nitride, diamond, and aluminum nitride.
4. The adhesive for semiconductors according to any one of claims 1 to 3, wherein,
the inorganic filler has peaks in the respective ranges of 0.1 to 4.5 μm and 5 to 20 μm in the volume-based particle size distribution.
5. The adhesive for semiconductors according to any one of claims 1 to 4, wherein,
the inorganic filler is blended with a volume-based average particle diameter r 1 Polyhedral alumina of 5 to 20 mu m and volume-based average particle diameter r 2 Polyhedral alumina of 0.1-4.5 μm.
6. The adhesive for semiconductors according to claim 5, wherein,
the average particle diameter r 1 With the average particle diameter r 2 The difference (r) between 1 -r 2 ) Is 4-10 μm.
7. The adhesive for semiconductors according to any one of claims 1 to 6, which has a thermal conductivity of 3.0W/mK or more after curing.
8. The adhesive for semiconductors according to any one of claims 1 to 7, wherein,
the fluxing agent is a carboxylic acid.
9. The adhesive for semiconductors according to any one of claims 1 to 8, wherein,
the curable resin component contains a thermosetting resin, a curing agent, and a thermoplastic resin.
10. A method of manufacturing a semiconductor device having a connection structure in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other and/or a connection structure in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, the method comprising:
a step of sealing at least a part of the connection part using the adhesive for semiconductors according to any one of claims 1 to 9.
11. A semiconductor device includes:
a connection structure in which respective connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other and/or a connection structure in which respective connection portions of the plurality of semiconductor chips are electrically connected to each other; and
a sealing material sealing at least a part of the connection portion,
the sealing material contains a cured product of the adhesive for semiconductors according to any one of claims 1 to 9.
CN202180021009.9A 2020-04-01 2021-03-25 Adhesive for semiconductor, semiconductor device and method for manufacturing the same Pending CN115298280A (en)

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