CN113348221B - Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device - Google Patents

Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device Download PDF

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Publication number
CN113348221B
CN113348221B CN201980090381.8A CN201980090381A CN113348221B CN 113348221 B CN113348221 B CN 113348221B CN 201980090381 A CN201980090381 A CN 201980090381A CN 113348221 B CN113348221 B CN 113348221B
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China
Prior art keywords
adhesive
film
component
adhesive composition
elastomer
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CN201980090381.8A
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Chinese (zh)
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CN113348221A (en
Inventor
桥本慎太郎
矢羽田达也
舛野大辅
谷口纮平
中村祐树
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Lishennoco Co ltd
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Lishennoco Co ltd
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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
    • 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
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer 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
    • H01L2224/32221—Disposition the layer 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
    • H01L2224/32225—Disposition the layer 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 non-metallic, e.g. insulating substrate with or without metallisation
    • 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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—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
    • H01L2224/48221—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
    • H01L2224/48225—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 non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—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 non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • 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
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8338—Bonding interfaces outside the semiconductor or solid-state body
    • H01L2224/83385—Shape, e.g. interlocking features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)
  • Die Bonding (AREA)

Abstract

The invention discloses an adhesive composition, which comprises a thermosetting resin, a curing agent and an elastomer, wherein the thermosetting resin comprises an epoxy resin with an alicyclic ring, and the elastomer comprises an elastomer with a carboxyl group. Also disclosed is a film-like adhesive using the adhesive composition. Also disclosed are an adhesive sheet using the film-like adhesive and a method for manufacturing a semiconductor device.

Description

Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device
Technical Field
The present invention relates to an adhesive composition, a film-like adhesive, an adhesive sheet, and a method for manufacturing a semiconductor device.
Background
Conventionally, silver paste has been mainly used for bonding a semiconductor chip to a support member for mounting the semiconductor chip. However, with the recent miniaturization and integration of semiconductor chips, miniaturization and refinement of support members used have been demanded. On the other hand, when silver paste is used, problems such as defects, difficulty in film thickness control, and void generation may occur in wire bonding due to overflow of paste or inclination of semiconductor chips.
Therefore, in recent years, a film-like adhesive (ad head) for bonding a semiconductor chip and a support member has been used (for example, refer to patent document 1). In the case of using an adhesive sheet including a dicing tape and a film-like adhesive laminated on the dicing tape, a film-like adhesive is attached to the back surface of a semiconductor wafer, and the semiconductor wafer is singulated by dicing, whereby a semiconductor chip with the film-like adhesive can be obtained. The obtained semiconductor chip with the film-like adhesive can be attached to a support member via the film-like adhesive and bonded by thermocompression bonding.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2007-053240
Disclosure of Invention
Technical problem to be solved by the invention
However, as the size of the semiconductor chip becomes smaller, a force applied per unit area at the time of thermocompression bonding becomes larger, and a phenomenon called bleed-out (bleed) may occur in which the film-like adhesive overflows from the semiconductor chip.
In addition, when a Film-like adhesive is used as a Wire wrapping Film (FOW) which is a Wire embedding type Film-like adhesive or a chip wrapping Film (FOD) which is a semiconductor chip embedding type Film-like adhesive, fluidity is required to be high at the time of thermocompression bonding from the viewpoint of improving embeddability. Therefore, the occurrence frequency and the amount of exudation tend to be further increased. Depending on the case, bleeding may sometimes occur to the upper surface of the semiconductor chip. Further, since the resin flows in the high-temperature pressurizing process after the thermocompression bonding, the amount of bleeding increases as compared with the thermocompression bonding, and thus electrical failure or wire bonding failure may occur.
The present invention has been made in view of such circumstances, and a main object thereof is to provide an adhesive composition which has excellent embeddability in thermocompression bonding and can suppress bleeding out in high-temperature pressure treatment.
Means for solving the technical problems
One aspect of the present invention provides an adhesive composition including a thermosetting resin including an epoxy resin having an alicyclic ring, a curing agent, and an elastomer including an elastomer having a carboxyl group. According to this adhesive composition, it is possible to suppress bleeding during high-temperature pressure treatment while having good embeddability during thermocompression bonding.
The curing agent may comprise a phenolic resin. And, the elastomer may include an acrylic resin.
The elastomer may also comprise an elastomer having no carboxyl groups.
The thermosetting resin may further contain an aromatic epoxy resin having no alicyclic ring. The aromatic epoxy resin having no alicyclic ring may be a liquid at 25 ℃.
The adhesive composition may further comprise an inorganic filler. And, the adhesive composition may further comprise a curing accelerator.
The adhesive composition is used for bonding a second semiconductor element by bonding the second semiconductor element to the first semiconductor element by bonding the first semiconductor element to a substrate via a first wire and embedding at least a part of the first wire in a semiconductor device.
Further, the present invention may relate to an application as an adhesive or an application for manufacturing an adhesive, the composition including a thermosetting resin including an epoxy resin having an alicyclic ring, a curing agent, and an elastomer, the adhesive being used for crimping a second semiconductor element and embedding at least a part of a first wire in a semiconductor device in which the first semiconductor element is connected to a substrate via the first wire and is wire-bonded, and the second semiconductor element is crimped on the first semiconductor element.
In another aspect, the present invention provides a film-like adhesive comprising the above adhesive composition formed into a film.
In another aspect, the present invention provides an adhesive sheet comprising a substrate and the above-described film-like adhesive disposed on the substrate.
The substrate may be a dicing tape. In this specification, an adhesive sheet in which a base material is a dicing tape is sometimes referred to as a "dicing/die-bonding (dicing-bonding) integrated adhesive sheet".
The adhesive sheet may further include a protective film laminated on a surface of the film-like adhesive opposite to the base material.
Further, in another aspect, the present invention provides a method of manufacturing a semiconductor device, comprising: a wire bonding step of electrically connecting the first semiconductor element to the substrate via the first wire; a lamination step of attaching the film-like adhesive to one surface of the second semiconductor element; and a die bonding step of bonding the second semiconductor element attached with the film-like adhesive by pressure via the film-like adhesive, thereby embedding at least a part of the first wire into the film-like adhesive.
The semiconductor device may be a wire-embedded type semiconductor device in which a first semiconductor chip is connected to a semiconductor substrate via a first wire by wire bonding, and a second semiconductor chip is bonded to the first semiconductor chip via an adhesive film by pressure bonding, so that at least a part of the first wire is embedded in the adhesive film; the first lead and the first semiconductor chip may be embedded in the adhesive film.
Effects of the invention
According to the present invention, an adhesive composition having good embeddability at the time of thermocompression bonding and capable of suppressing bleeding can be provided. Therefore, the Film adhesive formed by forming the adhesive composition into a Film can be effectively used as a Film Over Die (FOD) as a semiconductor chip embedded Film adhesive or a Wire Over Wire (FOW) as a Wire embedded Film adhesive. Further, according to the present invention, an adhesive sheet using such a film-like adhesive and a method for manufacturing a semiconductor device can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing a film-like adhesive according to an embodiment.
Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment.
Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment.
Fig. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment.
Fig. 5 is a schematic cross-sectional view showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment.
Fig. 6 is a schematic cross-sectional view showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment.
Fig. 7 is a schematic cross-sectional view showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment.
Fig. 8 is a schematic cross-sectional view showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment.
Fig. 9 is a schematic cross-sectional view showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment.
Detailed Description
Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. However, the present invention is not limited to the following embodiments.
In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto. The same applies to other similar expressions such as (meth) acryl.
[ adhesive composition ]
The adhesive composition of the present embodiment contains (a) a thermosetting resin, (B) a curing agent, and (C) an elastomer. The adhesive composition is thermosetting, is in a semi-cured (B-stage) state and can be in a fully cured (C-stage) state after being cured.
Component (A): thermosetting resin >, and process for producing the same
From the standpoint of adhesion, the thermosetting resin may contain an epoxy resin. The adhesive composition of the present embodiment contains (a-1) an epoxy resin having an alicyclic ring as a thermosetting resin.
The component (A-1) is a compound having an alicyclic ring and an epoxy group in the molecule. The epoxy group may be bonded to an alicyclic ring or a site other than an alicyclic ring of the compound via a single bond or a linking group (for example, an alkylene group, an oxyalkylene group, or the like). The compound may be a compound having an epoxy group formed together with 2 carbon atoms constituting an alicyclic ring (i.e., an alicyclic epoxy compound). The thermosetting resin contains the component (A-1), and thus has excellent embeddability in thermocompression bonding and can suppress bleeding in high-temperature pressure treatment.
The epoxy equivalent of the component (A-1) is not particularly limited, and may be 90 to 600g/eq, 100 to 500g/eq or 120 to 450g/eq. When the epoxy equivalent of the component (A-1) is within these ranges, better reactivity and fluidity tend to be obtained.
The component (A-1) may be any of epoxy resins represented by the following general formulae (1) to (4), for example.
In the formula (1), E represents an alicyclic ring, G represents a single bond or an alkylene group, R 1 Each independently represents a hydrogen atom or a monovalent hydrocarbon group. n1 represents an integer of 1 to 10, and m represents an integer of 1 to 3.
The number of carbon atoms of E may be 4 to 12, 5 to 11 or 6 to 10.E may be a single ring or multiple rings, but is preferably multiple rings, and more preferably dicyclopentadiene ring. The alkylene group in G may be an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group. G is preferably a single bond. R is R 1 The monovalent hydrocarbon group in (a) may be, for example, an alkyl group such as methyl, ethyl, propyl, butyl, or pentyl; aryl groups such as phenyl and naphthyl; heteroaryl groups such as pyridyl. R is R 1 Preferably a hydrogen atom.
The epoxy resin represented by the general formula (1) may be an epoxy resin represented by the following general formula (1 a).
In the formula (1 a), n1 has the same meaning as described above.
Examples of the commercial products of the epoxy resin represented by the general formula (1 a) include HP-7200L, HP-7200H, HP-7200 (both manufactured by DIC CORPORATION), XD-1000 (manufactured by Nippon Kay aku Co., ltd.).
In the formula (2), R 2 Represents a hydrocarbon group of valence 2.
R 2 The hydrocarbon group having a valence of 2 in (a) may be, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group; arylene groups such as phenylene and naphthylene; heteroarylenes such as pyridine group (Pyridolene group). R is R 2 An alkylene group having 1 to 5 carbon atoms is preferable.
Examples of the commercial products of the epoxy resin represented by the general formula (2) include CELLOXIDE 2021P, CELLOXIDE 2081 (all manufactured by Daicel Corporation).
In the formula (3), R 3 、R 4 And R is 5 Each independently represents a hydrocarbon group having a valence of 2.
As R 3 、R 4 And R is 5 The hydrocarbon group of 2 valency in (2) may be mentioned as R 2 The same groups as exemplified by the 2-valent hydrocarbon groups in (a).
Examples of the commercial products of the Epoxy resin represented by the general formula (3) include Syna-Epoxy28 (manufactured by SYANASIA).
In the formula (4), R 6 Represents a hydrogen atom or a 1-valent hydrocarbon group, and n2 represents an integer of 1 to 10.
As R 6 The hydrocarbon group of 1 valence in (B) may be mentioned as R 1 The same groups as those exemplified for the 1-valent hydrocarbon group in (a).
Examples of the commercial products of the epoxy resin represented by the general formula (4) include EHPE3150 (manufactured by Daicel Corporation).
From the viewpoint of heat resistance, the component (a-1) is preferably an epoxy resin represented by the general formula (1), more preferably an epoxy resin represented by the general formula (1 a).
The content of the component (A-1) may be 15 to 100% by mass based on the total amount of the component (A). The content of the component (A-1) may be 40% by mass or more, 50% by mass or more, or 60% by mass or more.
The content of the component (A-1) may be 5% by mass or more, 10% by mass or more, or 20% by mass or more based on the total amount of the adhesive composition. When the content of the component (a-1) is 5 mass% or more based on the total amount of the adhesive composition, the adhesive composition tends to have a better embeddability at the time of thermocompression bonding and can favorably suppress bleeding at the time of high-temperature pressure treatment.
In addition to the component (A-1), the component (A) may contain an aromatic epoxy resin having no alicyclic ring (A-2). Here, the aromatic epoxy resin having no alicyclic ring is a compound having an aromatic ring and an epoxy group in the molecule and having no alicyclic ring. Examples of the component (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, phenyl aralkyl type epoxy resin, aralkyl biphenyl type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatic type such as anthracene. These may be used singly or in combination of two or more. Of these, the (A-2) component may be a liquid at 25 ℃.
The epoxy equivalent of the component (A-2) is not particularly limited, and may be 90 to 600g/eq, 100 to 500g/eq or 120 to 450g/eq. When the epoxy equivalent of the component (A-2) is within these ranges, better reactivity and fluidity tend to be obtained.
The content of the component (A-2) may be 0 to 85% by mass based on the total amount of the component (A). The content of the component (A-2) may be 60 mass% or less, 50 mass% or less, or 40 mass% or less.
Component (B): curing agent >, a process for preparing the same
(B) The component (c) is not particularly limited, and a conventionally used curing agent can be used as the curing agent for the thermosetting resin. When the thermosetting resin contains an epoxy resin, examples of the component (B) include a phenol resin, an ester compound, an aromatic amine, an aliphatic amine, and an acid anhydride. These may be used singly or in combination of two or more. Among these, the component (B) may contain a phenolic resin from the viewpoints of reactivity and stability with time.
The phenolic resin is not particularly limited as long as it is a resin having a phenolic hydroxyl group in the molecule. Examples of the phenolic resin include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol a, bisphenol F, phenylphenol, and aminophenol, and/or naphthols such as α -naphthol, β -naphthol, and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde in the presence of an acidic catalyst; phenol aralkyl resins, naphthol aralkyl resins, biphenyl aralkyl phenol resins, phenyl aralkyl phenol resins, and the like synthesized from phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalene diol, phenol novolac, phenol, and the like, and/or naphthols and dimethoxy para-xylene or bis (methoxymethyl) biphenyl. These may be used singly or in combination of two or more. Among these, from the viewpoint of heat resistance, the phenolic resin is preferably a resin having a water absorption of 2 mass% or less and a heating mass reduction rate (temperature rise rate: 5 ℃/min, environment: nitrogen) of less than 5 mass% at 350 ℃ measured by a thermogravimetric analyzer (TGA) in a constant temperature and humidity tank at 85 ℃ and 85% rh for 48 hours.
Examples of the commercial products of the phenol resin include Phenolite KA series, TD series (manufactured by DIC CORPORATION), milex XLC series, XL series (manufactured by Mitsui Chemicals, inc. Manufactured by HE series (manufactured by AIR WATER INC), and the like.
The hydroxyl equivalent of the phenolic resin is not particularly limited and may be 80 to 400g/eq, 90 to 350g/eq or 100 to 300g/eq. When the hydroxyl equivalent of the phenolic resin is within these ranges, better reactivity and fluidity tend to be obtained.
From the viewpoint of curability, the ratio of the epoxy equivalent of the epoxy resin in the case where the component (a) is an epoxy resin and the hydroxyl equivalent of the phenolic resin in the case where the component (B) is a phenolic resin (epoxy equivalent of epoxy resin/hydroxyl equivalent of phenolic resin) may be 0.30/0.70 to 0.70/0.30, 0.35/0.65 to 0.65/0.35, 0.40/0.60 to 0.60/0.40 or 0.45/0.55 to 0.55/0.45. When the equivalent ratio is 0.30/0.70 or more, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70/0.30 or less, the viscosity can be prevented from becoming excessively high, and more sufficient fluidity can be obtained.
The total content of the component (a) and the component (B) may be 30 to 70% by mass based on the total amount of the adhesive composition. (A) The total content of the component (a) and the component (B) may be 33 mass% or more and 36 mass% or more and 40 mass% or more, and may be 65 mass% or less, 60 mass% or less and 55 mass% or less. If the total content of the component (a) and the component (B) is 30 mass% or more based on the total amount of the adhesive composition, the adhesiveness tends to be improved. When the total content of the component (a) and the component (B) is 70 mass% or less based on the total amount of the adhesive composition, the viscosity can be prevented from becoming too low and bleeding during the high-temperature pressure treatment can be further suppressed.
Component (C): elastomer >
The adhesive composition of the present embodiment contains (C) an elastomer. The adhesive composition of the present embodiment contains (C-1) an elastomer having a carboxyl group as an elastomer. (C) The component (c) is preferably a polymer constituting the elastomer and having a glass transition temperature (Tg) of 50 ℃ or lower.
The component (C-1) is a compound (elastomer) having a carboxyl group in the molecule. The elastomer contains the (C-1) component, and thus has excellent embeddability in thermocompression bonding and can suppress bleeding in high-temperature pressure treatment.
Examples of the component (C-1) include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, butadiene resins, acrylonitrile resins, and modified products thereof.
From the viewpoints of solubility in a solvent and fluidity, the (C-1) component may contain an acrylic resin having a carboxyl group. The acrylic resin herein refers to a polymer containing a constituent unit derived from a (meth) acrylate. The acrylic resin is preferably a polymer containing, as a constituent unit, a constituent unit derived from a (meth) acrylate having a carboxyl group and a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or the like. The acrylic resin may be an acrylate rubber such as a copolymer of (meth) acrylate and acrylonitrile.
The glass transition temperature (Tg) of the acrylic resin may be-50 to 50℃or-30 to 30 ℃. When the Tg of the acrylic resin is at least-50 ℃, the flexibility of the adhesive composition tends to be prevented from becoming too high. Thus, the film-like adhesive is easily cut when dicing the wafer, and burrs can be prevented from being generated. If the Tg of the acrylic resin is 50 ℃ or lower, the decrease in flexibility of the adhesive composition tends to be suppressed. Thus, when the film-like adhesive is attached to the wafer, the void tends to be easily and sufficiently buried. Further, chipping (chipping) at dicing due to a decrease in adhesion of the wafer can be prevented. Herein, the glass transition temperature (Tg) refers to a value measured using a DSC (thermal differential scanning calorimeter) (for example, rigaku Corporation manufactured "Thermo Plus 2").
The weight average molecular weight (Mw) of the acrylic resin may be 10 to 300 or 50 to 200. When the Mw of the acrylic resin is within these ranges, film formability, strength in the form of a film, flexibility, tackiness, and the like can be appropriately controlled, and the reflow property is excellent, so that the embeddability can be improved. Here, mw refers to a value measured by Gel Permeation Chromatography (GPC) and converted using a calibration curve based on standard polystyrene.
From the viewpoint of curability, the acid value of the component (C-1) may be 1 to 60mgKOH/g, 2 to 40mgKOH/g, or 3 to 30mgKOH/g. When the acid value is within these ranges, bleeding during high-temperature pressure treatment tends to be more suppressed.
Examples of the commercial products of the component (C-1) (acrylic resin) include SG-70L, SG-708-6, WS-023EK30 and SG-280EK23 (both manufactured by Nagase ChemteX corporation).
In addition to the component (C-1), the component (C) may contain an elastomer having no carboxyl group (C-2). The component (C-1) is a compound (elastomer) having no carboxyl group in the molecule.
Examples of the component (C-2) include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, butadiene resins, acrylonitrile resins, and modified products thereof.
From the viewpoints of solubility in a solvent and fluidity, the (C-2) component may contain an acrylic resin having no carboxyl group. Here, the acrylic resin refers to a polymer containing a constituent unit derived from (meth) acrylate. The acrylic resin is preferably a polymer containing a constituent unit derived from a (meth) acrylate having a crosslinkable functional group such as an epoxy group, an alcoholic hydroxyl group, or a phenolic hydroxyl group as a constituent unit. The acrylic resin may be an acrylate rubber such as a copolymer of (meth) acrylate and acrylonitrile.
The glass transition temperature (Tg) of the acrylic resin may be the same as the Tg of the acrylic resin of the (C-1) component. The weight average molecular weight (Mw) of the acrylic resin may be the same as the Mw of the acrylic resin of the (C-1) component.
Examples of the commercial products of the component (C-2) (acrylic resin) include SG-P3 and SG-80H (both produced by Nagase ChemteX corporation).
The content of the component (C) may be 20 to 200 parts by mass or 30 to 100 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). When the content of the component (C) is 20 parts by mass or more relative to 100 parts by mass of the total amount of the component (a) and the component (B), the handleability (e.g., bendability, etc.) of the film-like adhesive tends to be further improved. When the content of the component (C) is 200 parts by mass or less relative to 100 parts by mass of the total of the component (a) and the component (B), the flexibility of the adhesive composition tends to be further prevented from becoming too high. Thus, the film-like adhesive is easily cut when dicing the wafer, and burrs are prevented from being generated.
The mass ratio of the content of the component (C-1) to the content of the component (C) (the total content of the component (C-1) and the component (C-2)) (the content of the component (C-1)/the content of the component (C)) may be 0.05 to 1, 0.10 to 1, 0.20 to 1, 0.40 to 1 or 0.60 to 1.
Component (D): inorganic filler >, and
the adhesive composition of the present embodiment may further contain (D) an inorganic filler. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and the like. One kind of these may be used alone, or two or more kinds may be used in combination. From the viewpoint of further improving the thermal conductivity of the obtained film-like adhesive, the inorganic filler may contain alumina, aluminum nitride, boron nitride, crystalline silica, or amorphous silica. The inorganic filler may contain aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, or amorphous silica from the viewpoint of adjusting the melt viscosity of the adhesive composition and imparting thixotropic properties to the adhesive composition.
The average particle diameter of the component (D) may be 0.005 to 0.5 μm or 0.05 to 0.3. Mu.m, from the viewpoint of further improvement of the adhesion. The average particle diameter is a value obtained by conversion from the BET specific surface area.
The component (D) may be surface-treated with a surface treatment agent from the viewpoints of compatibility with a solvent, other components, and the like, and adhesive strength. Examples of the surface treatment agent include a silane coupling agent. Examples of the functional group of the silane coupling agent include a vinyl group, a (meth) acryl group, an epoxy group, a mercapto group, an amino group, a diamino group, an alkoxy group, and an ethoxy group.
The content of the component (D) may be 10 to 90 parts by mass or 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (a), the component (B), and the component (C). If the content of the component (D) is 10 parts by mass or more relative to 100 parts by mass of the total amount of the component (a), the component (B) and the component (C), the dicing property of the adhesive layer before curing tends to be improved and the adhesive force (bond force) of the adhesive layer after curing tends to be improved. When the content of the component (D) is 90 parts by mass or less relative to 100 parts by mass of the total amount of the component (a), the component (B) and the component (C), the film-like adhesive after curing can be prevented from having an excessively high elastic modulus while suppressing the decrease in fluidity.
Component (E): curing accelerator >, of
The adhesive composition of the present embodiment may contain (E) a curing accelerator. The curing accelerator is not particularly limited, and commonly used accelerators can be used. Examples of the component (E) include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like. These may be used singly or in combination of two or more. Among these, the component (E) may be imidazoles or derivatives thereof from the viewpoint of reactivity.
Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. These may be used singly or in combination of two or more.
The content of the component (E) may be 0.04 to 3 parts by mass or 0.04 to 0.2 part by mass relative to 100 parts by mass of the total amount of the component (A), the component (B), and the component (C). If the content of the component (E) is within these ranges, both curability and reliability tend to be achieved.
< other Components >)
The adhesive composition of the present embodiment may further contain an antioxidant, a silane coupling agent, a rheology control agent, and the like as other components. The content of these components may be 0.02 to 3 parts by mass per 100 parts by mass of the total amount of the components (a), (B) and (C).
The adhesive composition of the present embodiment may be used as an adhesive varnish diluted with a solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving components other than the component (D). Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-isopropyltoluene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1, 4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, gamma-butyrolactone and the like; carbonates such as ethylene carbonate and propylene carbonate; amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. These may be used singly or in combination of two or more. Among these, from the viewpoints of solubility and boiling point, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexane.
The concentration of the solid content in the adhesive varnish may be 10 to 80 mass% based on the total mass of the adhesive varnish.
The adhesive varnish can be prepared by mixing and kneading the component (a), the component (B), the component (C), the solvent, and if necessary, the component (D), the component (E), and other components. The mixing and kneading can be performed by appropriately combining a general stirrer, a grinding stirrer, a three-roll mill, a ball mill, a bead mill, or other dispersing machine. When the component (D) is contained, the time for mixing can be shortened by mixing the component (D) and the low-molecular-weight component in advance and then blending the high-molecular-weight component. Also, after the adhesive varnish is prepared, bubbles in the varnish may be removed by vacuum degassing or the like.
[ film-like adhesive ]
Fig. 1 is a schematic cross-sectional view showing a film-like adhesive according to an embodiment. The film-like adhesive 10 is an adhesive formed by forming the adhesive composition into a film. The film adhesive 10 may be in a semi-cured (B-stage) state. Such a film-like adhesive 10 can be formed by applying the adhesive composition to a support film. In the case of using an adhesive varnish, the adhesive varnish is applied to a support film, and then heated and dried to remove the solvent, whereby the film-like adhesive 10 can be formed.
The support film is not particularly limited, and examples thereof include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, and the like. The thickness of the support film may be, for example, 60 to 200 μm or 70 to 170 μm.
As a method of applying the adhesive varnish to the support film, known methods can be used, and examples thereof include knife coating, roll coating, spray coating, gravure coating, bar coating, curtain coating, and the like. The conditions for the heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 0.1 minutes to 90 minutes at 50 to 200 ℃.
The thickness of the film-like adhesive can be appropriately adjusted according to the application. The thickness of the film-like adhesive may be 20 to 200 μm, 30 to 200 μm, or 40 to 150 μm from the viewpoint of sufficiently embedding irregularities such as a semiconductor chip, a wire, a wiring circuit of a substrate, and the like.
[ adhesive sheet ]
Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment. The adhesive sheet 100 includes a substrate 20 and the film-like adhesive 10 described above disposed on the substrate.
The substrate 20 is not particularly limited, and may be a substrate film. The base film may be the same film as the support film described above.
The substrate 20 may also be a dicing tape. Such an adhesive sheet can be used as a dicing die-bonding integrated adhesive sheet. In this case, since the lamination process of the semiconductor wafer is performed once, efficiency of the operation can be improved.
Examples of the dicing tape include plastic films such as polytetrafluoroethylene films, polyethylene terephthalate films, polyethylene films, polypropylene films, polymethylpentene films, and polyimide films. The dicing tape may be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment, as required. The dicing tape is preferably a tape having tackiness. The dicing tape may be a tape that imparts tackiness to the plastic film, or may be a tape that has a pressure-sensitive adhesive layer provided on one side of the plastic film.
The adhesive sheet 100 can be formed by applying the adhesive composition to a substrate film in the same manner as the method of forming the film-like adhesive described above. The method of applying the adhesive composition to the substrate 20 may be the same as the method of applying the adhesive composition to the support film described above.
The adhesive sheet 100 may be formed using a film-shaped adhesive prepared in advance. In this case, the adhesive sheet 100 can be formed by laminating under a predetermined condition (for example, room temperature (20 ℃) or a heated state) using a roll laminator, a vacuum laminator, or the like. The adhesive sheet 100 is preferably formed in a heated state by using a roll laminator in view of continuous production and good efficiency.
The thickness of the film-like adhesive 10 may be 20 to 200 μm, 30 to 200 μm, or 40 to 150 μm from the viewpoint of embeddability of irregularities such as semiconductor chips, wires, wiring circuits of substrates, and the like. If the thickness of the film-like adhesive 10 is 20 μm or more, a more sufficient adhesive force tends to be obtained, and if the thickness of the film-like adhesive 10 is 200 μm or less, it is economical and can respond to the demand for miniaturization of semiconductor devices.
Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. The adhesive sheet 110 further includes a protective film 30 laminated on the surface of the film-like adhesive 10 opposite to the base material 20. The protective film 30 may be the same film as the support film described above. The thickness of the protective film may be, for example, 15 to 200 μm or 70 to 170 μm.
[ semiconductor device ]
Fig. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. The semiconductor device 200 is a semiconductor device in which a first semiconductor element Wa at a first stage is connected to a substrate 14 via a first wire 88 by wire bonding, and a second semiconductor element Wa is bonded to the first semiconductor element Wa via a film-like adhesive 10, whereby at least a part of the first wire 88 is embedded in the film-like adhesive 10. The semiconductor device may be a wire-embedded semiconductor device in which at least a part of the first wire 88 is embedded, or may be a semiconductor device in which the first wire 88 and the first semiconductor element Wa are embedded. In the semiconductor device 200, the substrate 14 is further electrically connected to the second semiconductor element Waa via the second wire 98, and the second semiconductor element Waa is encapsulated by the encapsulation material 42.
The thickness of the first semiconductor element Wa may be 10 to 170 μm and the thickness of the second semiconductor element Wa may be 20 to 400 μm. The first semiconductor element Wa buried inside the film-like adhesive 10 is a controller chip for driving the semiconductor device 200.
The substrate 14 includes the circuit pattern 84 and the circuit pattern 94, and the organic substrate 90 is formed at two positions on the surface. The first semiconductor element Wa is press-bonded to the circuit pattern 94 via the adhesive 41. The second semiconductor element Wa is bonded to the substrate 14 via the film-like adhesive 10 so as to cover the circuit pattern 94, the first semiconductor element Wa, and a part of the circuit pattern 84, which are not bonded to the first semiconductor element Wa. The film-like adhesive 10 is buried in the step of the irregularities caused by the circuit patterns 84 and 94 on the substrate 14. The second semiconductor element Waa, the circuit pattern 84, and the second wire 98 are encapsulated with the resin encapsulation material 42.
[ method for manufacturing semiconductor device ]
The method for manufacturing a semiconductor device according to the present embodiment includes: a first wire bonding step of electrically connecting the first semiconductor element to the substrate via the first wire; a lamination step of attaching the film-like adhesive to one surface of the second semiconductor element; and a die bonding step of bonding the second semiconductor element attached with the film-like adhesive by pressure via the film-like adhesive, thereby embedding at least a part of the first wire into the film-like adhesive.
Fig. 5 to 9 are schematic cross-sectional views showing a series of steps of a method for manufacturing a semiconductor device according to an embodiment. The semiconductor device 200 of the present embodiment is a semiconductor device in which the first wire 88 and the first semiconductor element Wa are embedded, and can be manufactured in the following order. First, as shown in fig. 5, the first semiconductor element Wa having the adhesive 41 is pressure-bonded on the circuit pattern 94 on the substrate 14, and the circuit pattern 84 on the substrate 14 is electrically bonded to the first semiconductor element Wa via the first wire 88 (first wire bonding process).
Next, the adhesive sheet 100 is laminated on one side of a semiconductor wafer (for example, 100 μm thick and 8 inches in size), and the base material 20 is peeled off, whereby the film-like adhesive 10 (for example, 110 μm thick) is attached on one side of the semiconductor wafer. Then, after the dicing tape is bonded to the film-like adhesive 10, the dicing tape is cut into a predetermined size (for example, 7.5mm square), and thereby, as shown in fig. 6, a second semiconductor element Waa to which the film-like adhesive 10 is attached is obtained (lamination step).
The temperature conditions of the lamination process may be 50 to 100℃or 60 to 80 ℃. When the temperature of the lamination step is 50 ℃ or higher, good adhesion to the semiconductor wafer can be obtained. When the temperature of the lamination step is 100 ℃ or lower, excessive flow of the film-like adhesive 10 during the lamination step can be suppressed, and thus, occurrence of thickness variation or the like can be prevented.
Examples of the dicing method include dicing with a blade having a rotating blade, and cutting the film-like adhesive or both the wafer and the film-like adhesive with a laser.
The second semiconductor element Waa to which the film-like adhesive 10 is attached is pressure-bonded to the substrate 14 to which the first semiconductor element Wa is bonded via the first wire 88. Specifically, as shown in fig. 7, the second semiconductor element Waa to which the film-like adhesive 10 is attached is mounted so as to cover the first wire 88 and the first semiconductor element Wa with the film-like adhesive 10, and then, as shown in fig. 8, the second semiconductor element Waa is fixed to the substrate 14 by pressure-bonding the second semiconductor element Waa to the substrate 14 (die bonding step). In the die bonding step, the film-like adhesive 10 is preferably pressure-bonded at 80 to 180 ℃ under 0.01 to 0.50MPa for 0.5 to 3.0 seconds. After the die bonding step, the film-like adhesive 10 is pressurized and heated at 60 to 175 ℃ and 0.3 to 0.7MPa for 5 minutes or more as a high-temperature pressurizing treatment.
Next, as shown in fig. 9, after the substrate 14 and the second semiconductor element Waa are electrically connected via the second wire 98 (second wire bonding step), the circuit pattern 84, the second wire 98, and the second semiconductor element Waa are encapsulated with the encapsulation material 42. By performing such a process, the semiconductor device 200 can be manufactured.
As another embodiment, the semiconductor device may be a wire-embedded semiconductor device in which at least a part of the first wire 88 is embedded.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
(examples 1 to 8 and comparative examples 1-1 to 1-3 and comparative examples 2 to 4)
< preparation of adhesive sheet >)
The following components were mixed in the blending ratios (parts by mass) shown in tables 1, 2 and 3, and a varnish of an adhesive composition having a solid content of 40% by mass was prepared using cyclohexanone as a solvent. Subsequently, the obtained varnish was filtered by a 100-mesh filter, and vacuum-exhausted. The vacuum-exhausted varnish was coated on a release-treated polyethylene terephthalate (PET) film having a thickness of 38 μm as a base film. The applied varnish was heat dried in two stages of 5 minutes at 90 ℃ followed by 5 minutes at 140 ℃. Thus, an adhesive sheet having a film-like adhesive having a thickness of 110 μm in a semi-cured (B-stage) state on a substrate film was obtained.
The components in tables 1, 2 and 3 are as follows.
(A) Thermosetting resin
(A-1) an epoxy resin having an alicyclic ring
A-1-1: an epoxy resin represented by the general formula (1 a) (an epoxy resin having a dicyclopentadiene structure), DIC CORPORATION, trade name: HP-7200L, epoxy equivalent: 250-280 g/eq
A-1-2: an epoxy resin represented by the general formula (1 a) (an epoxy resin having a dicyclopentadiene structure), nippon Kayaku co., ltd. XD-1000, epoxy equivalent: 254g/eq
A-1-3: an epoxy resin represented by the general formula (2) (liquid at 25 ℃), daicel Corpor ation, trade name: CELLOXIDE 2021P, epoxy equivalent: 128-145 g/eq
A-1-4: manufactured by epoxy resin represented by general formula (4), daicel Corporation, trade name: EHPE3150, epoxy equivalent: 170-190 g/eq
(A-2) an aromatic epoxy resin having no alicyclic ring
A-2-1: polyfunctional aromatic epoxy resin, printec Corporation, trade name: VG3101L, epoxy equivalent: 210g/eq
A-2-2: cresol novolac type epoxy resin, NIPPON STEEL Chemical & Material co., ltd., trade name: YDCN-700-10, epoxy equivalent: 209g/eq
A-2-3: bisphenol F type epoxy resin (liquid at 25 ℃), manufactured by DIC CORPORATION, trade name: EXA-830CRP, epoxy equivalent: 159g/eq
(B) Curing agent
B-1: bisphenol a novolac type phenolic resin manufactured by DIC CORPORATION, trade name: LF-4871, hydroxyl equivalent: 118g/eq
B-2: phenyl aralkyl type phenolic resin manufactured by Mitsui Chemicals, inc: XLC-LL, hydroxyl equivalent: 175g/eq
B-3: phenyl aralkyl type phenol resin, manufactured by AIR WATER INC, trade name: HE100C-30, hydroxyl equivalent: 170g/eq
(C) Elastic body
(C-1) an elastomer having carboxyl groups
C-1-1: carboxyl group-containing acrylic resin (acrylate rubber), manufactured by Nagase ChemteX corporation, trade name: SG-70L, weight average molecular weight: 90 ten thousand acid number: 5mgKOH/g, tg: 13 ℃ below zero
C-1-2: carboxyl group-containing acrylic resin (acrylate rubber), manufactured by Nagase ChemteX corporation, trade name: SG-708-6, weight average molecular weight: 70 ten thousand acid value: 9mgKOH/g, tg:4 DEG C
C-1-3: carboxyl group-containing acrylic resin (acrylate rubber), manufactured by Nagase ChemteX corporation, trade name: WS-023EK30, weight average molecular weight: 50 ten thousand acid value: 20mgKOH/g, tg: -10 DEG C
(C-2) an elastomer having no carboxyl group
C-2-1: epoxy group-containing acrylic resin (acrylate rubber) containing no carboxyl group, manufactured by Nagase ChemteX corporation, trade name: SG-P3 solvent modification, weight average molecular weight: 80 ten thousand, tg:12 DEG C
C-2-2: epoxy group-containing acrylic resin (acrylate rubber) containing no carboxyl group, manufactured by Nagase ChemteX corporation, trade name: SG-80H, weight average molecular weight: 35 ten thousand Tg:11 DEG C
(D) Inorganic filler
D-1: silica filler dispersion, fused silica, manufactured by Admatechs Company Limited, trade name: SC2050-HLG, average particle size: 0.50 μm
(E) Curing accelerator
E-1: 1-cyanoethyl-2-phenylimidazole, SHIKOKU CHEMICALS corporation, trade name: solid azole (Curezol) 2PZ-CN
< evaluation of various physical Properties >
The obtained adhesive sheet was evaluated for embeddability and bleeding amount.
[ evaluation of embedding Property ]
The following evaluation samples were prepared to evaluate the embeddability of the adhesive sheet. The film-like adhesive (thickness 110 μm) obtained above was peeled off the base film and attached to a dicing tape, to obtain a dicing die-bonding integrated adhesive sheet. Next, a semiconductor wafer (8 inches) having a thickness of 100 μm was heated to 70 ℃ and attached to the adhesive side. Thereafter, the semiconductor wafer was cut into 7.5mm squares, thereby obtaining semiconductor chips a. Next, a dicing die bonding integrated adhesive sheet (trade name: HR 9004-10) (thickness 10 μm) manufactured by Hitachi Chemical co., ltd was prepared, heated to 70 ℃ and attached to a semiconductor wafer (8 inches) having a thickness of 50 μm. Thereafter, the semiconductor wafer was cut into 4.5mm squares, whereby a semiconductor chip B with a die bonding film was obtained. Next, an evaluation substrate coated with a solder resist (manufactured by TAIYO NIPPON SANSO CORPORATION, trade name: AUS 308) was prepared and the total thickness was 260 μm, and the die bonding film of the semiconductor chip B with the die bonding film was pressure-bonded at 120 ℃ under 0.20MPa for 2 seconds so as to be in contact with the solder resist of the evaluation substrate. Thereafter, the film-like adhesive of the semiconductor chip a was pressed and bonded at 120 ℃ under 0.20MPa for 1.5 seconds so as to be in contact with the semiconductor wafer of the semiconductor chip B, thereby obtaining an evaluation sample. At this time, the alignment is performed so that the semiconductor chip B previously pressed is at the center of the semiconductor chip a. The evaluation sample obtained in this manner was subjected to observation of the presence or absence of voids by an ultrasonic digital image diagnostic apparatus (manufactured by site co., ltd. Manufactured by probe: 75 MHz), and when voids were observed, the ratio of the area of voids per unit area was calculated, and the analysis results were evaluated as embeddability. The evaluation criteria are as follows. The results are shown in tables 1, 2 and 3.
A: no voids were observed.
B: although voids were observed, the proportion was less than 5 area%.
C: voids were observed, and the proportion thereof was 5 area% or more.
[ evaluation of exudation amount ]
The samples evaluated as "a" or "B" in the above-mentioned embeddability evaluation were subjected to the bleeding amount evaluation. Samples were prepared in the same manner as the evaluation samples prepared in the above-described embeddability evaluation, and were subjected to a high-temperature pressure treatment (press curing) at 140℃under 0.7MPa for 30 minutes by a press oven to prepare exudation evaluation samples. The bleeding amount of the film-like adhesive was measured from the center of four sides of the evaluation sample using a microscope, and the maximum value thereof was set as the bleeding amount. The results are shown in tables 1, 2 and 3.
TABLE 1
TABLE 2
TABLE 3
As shown in table 1, the adhesive composition of example 1, which contains an epoxy resin having an alicyclic ring and an elastomer having a carboxyl group, maintained good embeddability and was able to suppress bleeding during high-temperature pressure treatment, as compared with the adhesive compositions of comparative examples 1-1 to 1-3, which did not contain these. From examples 2 and 3 of table 2 and examples 4 to 8 of table 3, it was found that the same tendency was observed even when an epoxy resin having another alicyclic ring was used or when an elastomer having another carboxyl group was used. From these results, it was confirmed that: the adhesive composition of the present invention has good embeddability at the time of thermocompression bonding, and can suppress bleeding at the time of high-temperature pressure treatment.
Industrial applicability
As shown in the above results, the adhesive composition of the present invention has good embeddability at the time of thermocompression bonding and can suppress bleeding at the time of high-temperature pressure treatment, and therefore, the Film-like adhesive formed by forming the adhesive composition into a Film can be effectively used as a Film Over Die (FOD) as a Die-embedded Film-like adhesive or a Wire Over Wire (FOW) as a Wire-embedded Film-like adhesive.
Symbol description
10-film-like adhesive, 14-substrate, 20-base material, 30-protective film, 41-adhesive, 42-encapsulating material, 84, 94-circuit pattern, 88-first wire, 90-organic substrate, 98-second wire, 100, 110-adhesive sheet, 200-semiconductor device, wa-first semiconductor element, wa-second semiconductor element.

Claims (11)

1. An adhesive composition comprising a thermosetting resin, a curing agent and an elastomer,
the thermosetting resin comprises an epoxy resin having an alicyclic ring and an aromatic epoxy resin having no alicyclic ring,
the curing agent comprises a phenolic resin and,
the elastomer comprises an elastomer having a carboxyl group,
the polymer constituting the elastomer has a glass transition temperature of 50 ℃ or lower,
The content of the alicyclic ring-free aromatic epoxy resin is 40 mass% or less based on the total amount of the thermosetting resin,
the total content of the thermosetting resin and the curing agent is 30 to 70 mass% based on the total amount of the adhesive composition.
2. The adhesive composition according to claim 1, wherein,
the elastomer comprises an acrylic resin.
3. The adhesive composition according to claim 1 or 2, wherein,
the elastomer also comprises an elastomer having no carboxyl groups.
4. The adhesive composition according to claim 1, wherein,
the aromatic epoxy resin having no alicyclic ring is liquid at 25 ℃.
5. The adhesive composition of claim 1 or 2, further comprising an inorganic filler.
6. The adhesive composition of claim 1 or 2, further comprising a cure accelerator.
7. A film-like adhesive comprising the adhesive composition according to any one of claims 1 to 6 formed into a film.
8. An adhesive sheet, comprising:
a substrate; and
The film-like adhesive of claim 7 disposed on the substrate.
9. The adhesive sheet according to claim 8, wherein,
The substrate is a dicing tape.
10. The adhesive sheet according to claim 8 or 9, further comprising a protective film laminated on a surface of the film-like adhesive opposite to the substrate.
11. A method of manufacturing a semiconductor device, comprising:
a wire bonding step of electrically connecting the first semiconductor element to the substrate via the first wire;
a lamination step of attaching the film-like adhesive according to claim 7 to one surface of the second semiconductor element; and
And a die bonding step of bonding a second semiconductor element to which the film-like adhesive is attached by pressure via the film-like adhesive, thereby embedding at least a part of the first wire into the film-like adhesive.
CN201980090381.8A 2019-01-28 2019-01-28 Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device Active CN113348221B (en)

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Application Number Priority Date Filing Date Title
PCT/JP2019/002789 WO2020157805A1 (en) 2019-01-28 2019-01-28 Adhesive composition, film-like adhesive, adhesive sheet and method for producing semiconductor device

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