CN102190864A - 半导体密封填充用环氧树脂组合物、半导体装置及其制造方法 - Google Patents

半导体密封填充用环氧树脂组合物、半导体装置及其制造方法 Download PDF

Info

Publication number
CN102190864A
CN102190864A CN2011100518708A CN201110051870A CN102190864A CN 102190864 A CN102190864 A CN 102190864A CN 2011100518708 A CN2011100518708 A CN 2011100518708A CN 201110051870 A CN201110051870 A CN 201110051870A CN 102190864 A CN102190864 A CN 102190864A
Authority
CN
China
Prior art keywords
acid
epoxy resin
substrate
semi
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011100518708A
Other languages
English (en)
Inventor
榎本哲也
宫泽笑
本田一尊
永井朗
大久保惠介
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Denko Materials Co ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN102190864A publication Critical patent/CN102190864A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—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
    • H01L24/83—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/13109—Indium [In] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/13111—Tin [Sn] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/13139—Silver [Ag] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/13144—Gold [Au] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/13147—Copper [Cu] as principal constituent
    • 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
    • H01L2224/27—Manufacturing methods
    • H01L2224/273—Manufacturing methods by local deposition of the material of the layer connector
    • H01L2224/2731—Manufacturing methods by local deposition of the material of the layer connector in liquid form
    • H01L2224/27312—Continuous flow, e.g. using a microsyringe, a pump, a nozzle or extrusion
    • 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
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • 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
    • H01L2224/731—Location prior to the connecting process
    • H01L2224/73101—Location prior to the connecting process on the same surface
    • H01L2224/73103—Bump and layer connectors
    • H01L2224/73104—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • 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
    • H01L2224/81—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 bump connector
    • H01L2224/8119—Arrangement of the bump connectors prior to mounting
    • H01L2224/81193—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed on both the semiconductor or solid-state body and another item or body to be connected to 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
    • H01L2224/81—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 bump connector
    • H01L2224/812—Applying energy for connecting
    • H01L2224/81201—Compression bonding
    • H01L2224/81203—Thermocompression bonding, e.g. diffusion bonding, pressure joining, thermocompression welding or solid-state welding
    • H01L2224/81204—Thermocompression bonding, e.g. diffusion bonding, pressure joining, thermocompression welding or solid-state welding with a graded temperature profile
    • 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
    • H01L2224/81—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 bump connector
    • H01L2224/812—Applying energy for connecting
    • H01L2224/8121—Applying energy for connecting using a reflow oven
    • 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
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to 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
    • H01L2224/832—Applying energy for connecting
    • H01L2224/8321—Applying energy for connecting using a reflow oven
    • 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
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H01L2224/83862—Heat curing
    • 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
    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/921—Connecting a surface with connectors of different types
    • H01L2224/9211—Parallel connecting processes
    • 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
    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/921—Connecting a surface with connectors of different types
    • H01L2224/9212—Sequential connecting processes
    • H01L2224/92122—Sequential connecting processes the first connecting process involving a bump connector
    • H01L2224/92125—Sequential connecting processes the first connecting process involving a bump connector the second connecting process involving a layer connector
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01023—Vanadium [V]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01032—Germanium [Ge]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01049—Indium [In]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01056—Barium [Ba]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01082—Lead [Pb]
    • 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
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • 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
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • 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
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1032—III-V
    • H01L2924/10329—Gallium arsenide [GaAs]
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Wire Bonding (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

本发明为半导体密封填充用环氧树脂组合物、半导体装置及其制造方法。本发明提供一种储存稳定性优异、且能够充分抑制在进行倒装片连接时产生孔隙、可以获得良好的连接可靠性的半导体密封填充用环氧树脂组合物、以及使用该组合物的半导体装置及其制造方法。本发明的半导体密封填充用环氧树脂组合物以环氧树脂、酸酐、固化促进剂、助熔剂为必须成分，固化促进剂是季鏻盐。本发明还提供使用该半导体密封填充用环氧树脂组合物的半导体装置及其制造方法。

Description

半导体密封填充用环氧树脂组合物、半导体装置及其制造方法
技术领域
本发明涉及半导体密封填充用环氧树脂组合物、半导体装置及其制造方法。
背景技术
近年，随着电子机器的小型化、高性能化，对半导体装置要求小型化、薄型化和电气特性的提高(对高频传输的应对等)。随之，开始从以往的通过引线接合将半导体芯片安装于基板上的方式向在半导体芯片上形成被称为凸块的导电性突起电极而与基板电极直接连接的倒装片连接方式转变。
作为半导体芯片上形成的凸块，使用的是由焊锡、金构成的凸块，但为了应对近年的微细连接化，开始使用在铜凸块的前端形成有焊锡的结构的凸块。
另外，为了高可靠性化，要求通过金属接合进行的连接，不仅是使用焊锡凸块的C4连接、利用在铜凸块的前端形成有焊锡的结构的凸块进行的焊锡接合，就是使用金凸块的情况下，也采用在基板电极侧形成焊锡，进行金-焊锡接合的连接方法。
进而，在倒装片连接方式中，有可能发生源于半导体芯片和基板的热膨胀系数差的热应力集中在连接部而破坏连接部的情况，因此，为了分散该热应力而提高连接可靠性，需要将半导体芯片和基板之间的空隙用树脂密封填充。通常，树脂的密封填充采用如下方式：用焊锡等连接半导体芯片和基板后，利用毛细管现象向空隙中注入液状密封树脂。
连接芯片和基板时，为了还原除去焊锡表面的氧化膜而容易地进行金属接合，通常使用由松香或有机酸等形成的助熔剂(flux)。这里，如果助熔剂的残渣残留，则在注入液状密封树脂时会成为产生被称为孔隙的气泡的原因，或者由于酸成分而发生配线的腐蚀，连接可靠性降低，因此，清洗残渣的工序是必须的。但是，随着连接间距的窄间距化，半导体芯片与基板之间的空隙变窄，因此有难以清洗助熔剂残渣的情况。而且，存在为了向半导体芯片和基板之间的狭窄孔隙中注入液状密封树脂，需要很长时间、生产性降低的问题。
为了解决这种液状密封树脂的问题，提出了被称为先供给方式的连接方法以及先供给方式所对应的密封树脂，所述先供给方式是：使用具有会还原除去焊锡表面的氧化膜的性质(助熔剂活性)的密封树脂，将密封树脂供给基板后，在连接半导体芯片和基板的同时，用树脂密封填充半导体芯片和基板之间的空隙，能够省略助熔剂残渣的清洗(例如，参照专利文献1～4)。
现有技术文献
专利文献1：日本特开2007-107006号公报
专利文献2：日本特开2007-284471号公报
专利文献3：日本特开2007-326941号公报
专利文献4：日本特开2009-203292号公报
发明内容
发明要解决的问题
但是，先供给方式中，由于密封树脂被暴露于进行焊锡接合时的高温连接条件，因此存在产生孔隙，使连接可靠性降低的问题。
另外，在高温连接条件下进行了焊锡接合后，在冷却至室温的过程中，由于半导体芯片和基板的热膨胀系数差而产生的热应力集中在连接部，为了使连接部不产生裂缝等，在焊锡接合时，需要使密封树脂进行固化来增强连接部。对此，如果使密封树脂的反应性提高，则在发生焊锡接合前密封树脂就固化了，会有发生连接不良，或者密封树脂的储存稳定性降低的问题。
因此，本发明的目的在于：提供储存稳定性优异、且在倒装片连接时孔隙的产生被充分抑制、可以得到良好的连接可靠性的半导体密封填充用环氧树脂组合物，以及使用了该环氧树脂组合物的半导体装置及其制造方法。
解决问题的手段
本发明提供一种以环氧树脂、酸酐、固化促进剂、助熔剂为必须成分，且固化促进剂是季鏻盐的半导体密封填充用环氧树脂组合物(以下，也简称为“环氧树脂组合物”)。
通过所述半导体密封填充用环氧树脂组合物，储存稳定性优异，且在倒装片连接时孔隙的产生被充分抑制，可以得到良好的连接可靠性。
从可以进一步提高储存稳定性的观点考虑，上述季鏻盐优选为四烷基鏻盐或四芳基鏻盐。
为了实现低热膨胀化，优选上述环氧树脂组合物进一步含有无机填料。
从可以提高操作性的观点考虑，优选上述环氧树脂组合物被形成为膜状。
本发明还提供一种半导体装置的制造方法，其包括：将上述环氧树脂组合物供给到半导体芯片或基板上的第一工序；以及，对半导体芯片和基板进行位置对准后，对半导体芯片和基板进行倒装片连接，同时将半导体芯片和基板之间的空隙用环氧树脂组合物密封填充的第二工序。
进而，本发明提供一种半导体装置，其具备：基板、与该基板电连接的半导体芯片、以及密封所述基板和所述半导体芯片之间的空隙的密封树脂，该树脂由上述环氧树脂组合物的固化物形成。
所述半导体装置由于使用本发明的环氧树脂组合物，因此连接可靠性优异。
发明效果
根据本发明，可以提供储存稳定性优异、且在倒装片连接时孔隙的产生被充分抑制、可以得到良好的连接可靠性的半导体密封填充用环氧树脂组合物，以及使用了该环氧树脂组合物的半导体装置及其制造方法。
附图说明
图1是表示本发明的半导体装置的一个实施方式的剖视图。
符号说明
1...焊锡球，2...电极垫片，3...凸块，4...配线，5...半导体芯片，6...密封树脂，7...电路基板，10...半导体装置。
具体实施方式
本发明的环氧树脂组合物以环氧树脂、酸酐、助熔剂、固化促进剂为必须成分。
作为环氧树脂，只要是2官能以上的环氧树脂，则没有特别限定，例如可以使用双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、联苯型环氧树脂、氢醌型环氧树脂、含二苯硫醚骨架的环氧树脂、酚芳烷基型多官能环氧树脂、含萘骨架的多官能环氧树脂、含二环戊二烯骨架的多官能环氧树脂、含三苯基甲烷骨架的多官能环氧树脂、氨基酚型环氧树脂、二氨基二苯基甲烷型环氧树脂、其他各种多官能环氧树脂。这些之中，从低粘度化、低吸水率、高耐热性的观点考虑，优选使用双酚A型环氧树脂、双酚F型环氧树脂、含萘骨架的多官能环氧树脂、含二环戊二烯骨架的多官能环氧树脂、含三苯基甲烷骨架的多官能环氧树脂。另外，对于这些环氧树脂的性状而言，在25℃是液态还是固态都没有关系，如果是固态的环氧树脂，例如在使焊锡加热熔融进行连接的情况下，优选使用熔点或软化点低于焊锡熔点的环氧树脂。另外，这些树脂可以单独使用或将2种以上混合使用。
作为酸酐，例如可以使用马来酸酐、琥珀酸酐、十二烯基琥珀酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、桥亚甲基四氢邻苯二甲酸酐、甲基桥亚甲基四氢邻苯二甲酸酐、甲基纳迪克酸酐(himic anhydride)、均苯四酸二酐、二苯甲酮四羧酸二酐、聚壬二酐、烷基苯乙烯-马来酸酐共聚物、3，4-二甲基-6-(2-甲基-1-丙烯基)-4-环己烯-1，2-二羧酸酐、1-异丙基-4-甲基-双环[2.2.2]辛-5-烯-2，3-二羧酸酐、乙二醇二偏苯三酸酐酯、丙三醇三偏苯三酸酐酯。这些之中，尤其是从耐热性、耐湿性的观点考虑，优选使用甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、桥亚甲基四氢邻苯二甲酸酐、甲基桥亚甲基四氢邻苯二甲酸酐、3，4-二甲基-6-(2-甲基-1-丙烯基)-4-环己烯-1，2-二羧酸酐、1-异丙基-4-甲基-双环[2.2.2]辛-5-烯-2，3-二羧酸酐、乙二醇二偏苯三酸酐酯、丙三醇三偏苯三酸酐酯。这些可以单独使用或将2种以上混合使用。
作为酸酐的配合量，优选按照与环氧树脂的当量比(环氧基的数量与由酸酐产生的羧基的数量之比：环氧基数量/羧基数量)为0.5～1.5的量来配合，更优选0.7～1.2。如果当量比小于0.5，则羧基过量残留，可能会有吸水率升高或耐湿可靠性降低的情况；如果当量比大于1.5，则可能会有固化不充分进行的情况。
作为助熔剂，优选使用从醇类、酚类、羧酸类中选择的至少一种化合物。
醇类优选是分子内具有至少2个以上醇羟基的化合物。作为其具体例子，可以举出1，3-二氧六环-5，5-二甲醇、1，5-戊二醇、2，5-呋喃二甲醇、二乙二醇、四乙二醇、五乙二醇、六乙二醇、1，2，3-己三醇、1，2，4-丁三醇、1，2，6-己三醇、3-甲基戊烷-1，3，5-三醇、丙三醇、三羟甲基乙烷、三羟甲基丙烷、赤藓醇、季戊四醇、核糖醇、山梨糖醇、2，4-二乙基-1，5-戊烷二醇、丙二醇单甲基醚、丙二醇单乙基醚、1，3-丁二醇、2-乙基-1，3-己烷二醇、N-丁基二乙醇胺、N-乙基二乙醇胺、二乙醇胺、三乙醇胺、N，N-双(2-羟基乙基)异丙醇胺、双(2-羟基甲基)亚氨基三(羟基甲基)甲烷、N，N，N’，N’-四(2-羟基乙基)乙二胺、1，1’，1”，1”’-(亚乙基二硝基)四(2-丙醇)。这些化合物可以单独使用，也可以将2种以上组合使用。
酚类优选是具有至少2个以上酚羟基的化合物。作为其具体例子，可以举出邻苯二酚、间苯二酚、对苯二酚、联苯酚、二羟基萘、羟基对苯二酚、邻苯三酚、亚甲基联苯酚(双酚F)、亚异丙基联苯酚(双酚A)、亚乙基联苯酚(双酚AD)、1，1，1-三(4-羟基苯基)乙烷、三羟基二苯甲酮、三羟基苯乙酮、聚对乙烯基苯酚。而且，作为具有至少2个以上酚羟基的化合物，还可以使用：从分子内具有至少1个以上酚羟基的化合物中选择的至少1种以上的化合物与从分子内具有2个卤代甲基、烷氧基甲基或羟基甲基的芳香族化合物、二乙烯基苯和醛类中选择的至少1种以上的化合物的缩聚物。
作为分子内具有至少1个以上酚羟基的化合物，例如可以举出苯酚、烷基苯酚、萘酚、甲酚、邻苯二酚、间苯二酚、对苯二酚、联苯酚、二羟基萘、羟基对苯二酚、邻苯三酚、亚甲基联苯酚(双酚F)、亚异丙基联苯酚(双酚A)、亚乙基联苯酚(双酚AD)、1，1，1-三(4-羟基苯基)乙烷、三羟基二苯甲酮、三羟基苯乙酮、聚对乙烯基苯酚。
另外，作为分子内具有2个卤代甲基、烷氧基甲基或羟基甲基的芳香族化合物，例如可以举出1，2-双(氯甲基)苯、1，3-双(氯甲基)苯、1，4-双(氯甲基)苯、1，2-双(甲氧基甲基)苯、1，3-双(甲氧基甲基)苯、1，4-双(甲氧基甲基)苯、1，2-双(羟基甲基)苯、1，3-双(羟基甲基)苯、1，4-双(羟基甲基)苯、双(氯甲基)联苯、双(甲氧基甲基)联苯。
作为醛类，例如可以举出甲醛(其水溶液福尔马林)、多聚甲醛、三噁烷、六亚甲基四胺。
作为缩聚物，例如可以举出作为苯酚与甲醛的缩聚物的苯酚酚醛清漆树脂、作为甲酚与甲醛的缩聚物的甲酚酚醛清漆树脂、作为萘酚类与甲醛的缩聚物的萘酚酚醛清漆树脂、作为苯酚与1，4-双(甲氧基甲基)苯的缩聚物的苯酚芳烷基树脂、双酚A与甲醛的缩聚物、苯酚与二乙烯基苯的缩聚物、甲酚与萘酚与甲醛的缩聚物，也可以是这些缩聚物经橡胶改性后的物质、或分子骨架内导入有氨基三嗪骨架或二环戊二烯骨架的物质。
另外，作为这些化合物的性状，在室温下可以是固体状也可以是液状，但为了均匀地还原除去金属表面的氧化膜，不阻碍焊锡的润湿性，优选使用液状，例如，作为通过将这些具有酚羟基的化合物烯丙基化而成为液状的物质，可以举出烯丙基化苯酚酚醛清漆树脂、二烯丙基双酚A、二烯丙基双酚F、二烯丙基联苯酚。这些化合物可以单独使用，可以将2种以上组合使用。
作为羧酸类，可为脂肪族羧酸、芳香族羧酸中的任一，优选在25℃是固体状的羧酸。
作为脂肪族羧酸，例如可以举出丙二酸、甲基丙二酸、二甲基丙二酸、乙基丙二酸、烯丙基丙二酸、2，2’-硫代二乙酸、3，3’-硫代二丙酸、2，2’-(亚乙基二硫代)二乙酸、3，3’-二硫代二丙酸、2-乙基-2-羟基丁酸、二硫代二甘醇酸、二甘醇酸、乙炔二羧酸、马来酸、苹果酸、2-异丙基苹果酸、酒石酸、衣康酸、1，3-丙酮二羧酸、丙三羧酸(トリカルバリン酸，tricarballylic acid)、粘康酸、β-氢粘康酸、琥珀酸、甲基琥珀酸、二甲基琥珀酸、戊二酸、α-酮戊二酸、2-甲基戊二酸、3-甲基戊二酸、2，2-二甲基戊二酸、3，3-二甲基戊二酸、2，2-双(羟基甲基)丙酸、柠檬酸、己二酸、3-叔丁基己二酸、庚二酸、苯基乙二酸、苯基乙酸、硝基苯基乙酸、苯氧基乙酸、硝基苯氧基乙酸、苯基硫代乙酸、羟基苯基乙酸、二羟基苯基乙酸、扁桃酸、羟基扁桃酸、二羟基扁桃酸、1，2，3，4-丁烷四羧酸、辛二酸、4，4’-二硫代二丁酸、桂皮酸、硝基桂皮酸、羟基桂皮酸、二羟基桂皮酸、香豆酸、苯基丙酮酸、羟基苯基丙酮酸、咖啡酸、高邻苯二酸、甲苯乙酸、苯氧基丙酸、羟基苯基丙酸、苄氧乙酸、苯基乳酸、托品酸、3-(苯基磺酰基)丙酸、3，3-四亚甲基戊二酸、5-氧代壬二酸、壬二酸、苯基琥珀酸、1，2-亚苯基二乙酸、1，3-亚苯基二乙酸、1，4-亚苯基二乙酸、苄基丙二酸、癸二酸、十二烷二酸、十一烷二酸、二苯基乙酸、二苯乙醇酸、二环己基乙酸、十四烷二酸、2，2-二苯基丙酸、3，3-二苯基丙酸、4，4-双(4-羟基苯基)吉草酸、海松酸、长叶松酸、异海松酸、松香酸、脱氢松香酸、新松香酸、阿盖二羧酸。
作为芳香族羧酸，例如可以举出安息香酸、2-羟基安息香酸、3-羟基安息香酸、4-羟基安息香酸、2，3-二羟基安息香酸、2，4-二羟基安息香酸、2，5-二羟基安息香酸、2，6-二羟基安息香酸、3，4-二羟基安息香酸、2，3，4-三羟基安息香酸、2，4，6-三羟基安息香酸、3，4，5-三羟基安息香酸、1，2，3-苯三羧酸、1，2，4-苯三羧酸、1，3，5-苯三羧酸、2-[双(4-羟基苯基)甲基]安息香酸、1-萘甲酸、2-萘甲酸、1-羟基-2-萘甲酸、2-羟基-1-萘甲酸、3-羟基-2-萘甲酸、6-羟基-2-萘甲酸、1，4-二羟基-2-萘甲酸、3，5-二羟基-2-萘甲酸、3，7-二羟基-2-萘甲酸、2，3-萘二羧酸、2，6-萘二羧酸、2-苯氧基安息香酸、联苯-4-羧酸、联苯-2-羧酸、2-苯甲酰基安息香酸。
其中，从储存安定性、容易购得的观点考虑，优选使用琥珀酸、苹果酸、衣康酸、2，2-双(羟基甲基)丙酸、己二酸、3，3，-硫代二丙酸、3，3，-二硫代二丙酸、1，2，3，4-丁烷四羧酸、辛二酸、癸二酸、苯基琥珀酸、十二烷二酸、二苯基乙酸、二苯乙醇酸、4，4-双(4-羟基苯基)吉草酸、松香酸、2，5-二羟基安息香酸、3，4，5-三羟基安息香酸、1，2，4-苯三羧酸、1，3，5-苯三羧酸、2-[双(4-羟基苯基)甲基]安息香酸。这些化合物可以单独使用，也可以将2种以上组合使用。
这些助熔剂的配合量，相对于环氧树脂和酸酐的总量100质量份，优选为0.1～15质量份，更优选为0.5～10质量份，进一步优选为1～10质量份。配合量少于0.1质量份时，会有焊锡表面的氧化膜除去效果表现不充分的倾向，超过15质量份时，有可能助熔剂的羧基和环氧树脂反应，储存稳定性降低。
作为固化促进剂，只要是季鏻盐就没有特别限定，例如可以使用四甲基鏻盐、四乙基鏻盐、四丁基鏻盐这样的四烷基鏻盐或四苯基鏻盐这样的四芳基鏻盐、三芳基膦类或三烷基膦类与1，4-苯醌的加成物。例如可以举出四苯基溴化鏻、四(正丁基)溴化鏻、四(4-甲基苯基)溴化鏻、甲基三苯基溴化鏻、乙基三苯基溴化鏻、甲氧基甲基三苯基氯化鏻、苄基三苯基氯化鏻、四(正丁基)鏻四氟硼酸盐、正十六烷基三(正丁基)鏻四氟硼酸盐、四苯基鏻四氟硼酸盐、四(正丁基)鏻四苯基硼酸盐、四苯基鏻四苯基硼酸盐、四苯基鏻四(4-甲基苯基)硼酸盐、四苯基鏻四(4-氟苯基)硼酸盐、四(正丁基)鏻苯并三唑盐、四(正丁基)鏻二乙基二硫代磷酸盐、三苯基膦与1，4-苯醌的加成物、三(4-甲基苯基)膦与1，4-苯醌的加成物、三(正丁基)膦与1，4-苯醌的加成物、三(环己基)膦与1，4-苯醌的加成物。这些之中，从杂质离子、储存稳定性的观点考虑，四(正丁基)鏻盐四氟硼酸盐、正十六烷基三(正丁基)鏻四氟硼酸盐、四苯基鏻四氟硼酸盐、四(正丁基)鏻四苯基硼酸盐、四苯基鏻四苯基硼酸盐、四苯基鏻四(4-甲基苯基)硼酸盐、四苯基鏻四(4-氟苯基)硼酸盐是合适的。另外，使用广泛用作固化促进剂的叔胺类或咪唑类时，与使用季鏻盐的情况相比，储存稳定性降低。
这些季磷盐的配合量，相对于环氧树脂和酸酐的总量100质量份，优选为0.01～10质量份，更优选0.1～5质量份。如果配合量少于0.01质量份，则可能固化性降低，连接可靠性降低；如果多于10质量份，则储存稳定性可能降低。
环氧树脂组合物的250℃时的凝胶化时间优选为3～30秒，更优选为3～20秒，进一步优选为3～15秒。如果比3秒短，则可能在焊锡熔融之前就发生固化，如果比30秒长，则可能生产性降低，或固化变得不充分。这里，凝胶化时间，是指将环氧树脂组合物放在设定为250℃的热板上，用刮勺等搅拌，直至不能搅拌的时间。
环氧树脂组合物在室温下可以是糊状，也可以是膜状，但从操作性的观点考虑，优选制成膜状。
对于环氧树脂组合物而言，为了形成膜状，也可以含有热塑性树脂。作为热塑性树脂，例如可以举出苯氧树脂、聚酰亚胺树脂、聚酰胺树脂、聚碳化二亚胺树脂、酚醛树脂、氰酸酯树脂、丙烯酸树脂、聚酯树脂、聚乙烯树脂、聚醚砜树脂、聚醚酰亚胺树脂、聚乙烯醇缩乙醛树脂、聚乙烯醇缩丁醛树脂、聚氨酯树脂、聚氨酯酰亚胺树脂、丙烯酸橡胶，其中，优选耐热性和成膜性优异的苯氧树脂、聚酰亚胺树脂、聚乙烯醇缩丁醛树脂、聚氨酯酰亚胺树脂、丙烯酸橡胶，更优选苯氧树脂、聚酰亚胺树脂。作为重均分子量，优选大于5000，更优选为10000以上，进一步优选为20000以上，在为5000以下时，会有成膜能力降低的情况。这里，重均分子量是使用GPC(Gel PermeationChromatography，凝胶渗透色谱)，以聚苯乙烯换算而测定得到的值。另外，这些热塑性树脂可以单独使用，也可以作为2种以上的混合物或共聚物来使用。
这些热塑性树脂的配合量，相对于环氧树脂和酸酐的总量100质量份，优选为5～200质量份，更优选为15～175质量份，进一步优选为25～150质量份。如果少于5质量份，则可能成膜性降低，操作变难；如果超过200质量份，则可能耐热性、可靠性降低。
进而，为了调整粘度、控制固化物的物性，环氧树脂组合物也可含有填料。填料可以是有机填料、无机填料中的任一，尤其是作为半导体密封填充用树脂组合物而使用时，为了实现低热膨胀化，优选含无机填料。
作为无机填料，例如可以举出玻璃、二氧化硅(silica)、氧化铝(alumina)、氧化钛(titania)、氧化镁(magnesia)、炭黑、云母、硫酸钡。这些可以单独使用或者2种以上混合使用。另外，无机填料也可以是含2种以上的金属氧化物的复合氧化物(不是2种以上的金属氧化物简单混合而成的，而是金属氧化物彼此发生化学性结合而成为不能分离的状态)。作为其具体例子，可以举出二氧化硅和氧化钛、二氧化硅和氧化镁、氧化硼和氧化铝、二氧化硅和氧化铝和氧化镁等形成的复合氧化物。
填料的形状可以是破碎状、针状、鳞片状、球状，没有特别限定，但从分散性和粘度控制的观点考虑，优选使用球状填料。另外，对于填料的尺寸而言，只要是其平均粒径比倒装片连接时的半导体芯片和基板之间的空隙小即可，从填充密度和粘度控制的观点考虑，优选平均粒径10μm以下，更优选平均粒径5μm以下，特别优选3μm以下。进而，为了调整粘度和固化物的物性，也可以将2种以上粒径不同的填料组合使用。
填料的配合量，相对于环氧树脂和酸酐的总量100质量份，优选设为200质量份以下，更优选设为175质量份以下。如果该配合量多于200质量份，则会有树脂组合物的粘度增高的倾向。
进而，环氧树脂中也可以配合硅烷偶联剂、钛偶联剂、抗氧化剂、流平剂、离子捕捉剂等添加剂。这些添加剂可以单独使用，也可以2种以上组合使用。对于配合量，调整为可显现出各添加剂的效果即可。
就环氧树脂组合物而言，可以用行星式混合机、擂溃机、珠磨机等对环氧树脂、酸酐、助熔剂、固化促进剂进行搅拌混合来使用。另外，配合填料的情况下，可以用3辊机进行混炼，使填料分散在树脂组合物中。
环氧树脂组合物例如可以通过以下所示的方法制成膜状(膜状树脂组合物)。
使用行星式混合机或珠磨机，在甲苯、乙酸乙酯、甲基乙基酮、环己酮、N-甲基吡咯烷酮等有机溶剂中，将热塑性树脂、环氧树脂、酸酐、助熔剂、固化促进剂、填料和其他添加剂混合，从而调制成清漆。采用刮刀涂布机或辊涂机，将得到的清漆涂布在实施了脱模处理的聚对苯二甲酸乙二醇酯等膜基材上，然后干燥除去有机溶剂，从而得到膜状树脂组合物。
接着，对于用本发明的环氧树脂组合物制造的半导体装置进行说明。
图1是表示本发明的半导体装置的一个实施方式的剖视图。图1所示的半导体装置10具有电路基板7、半导体芯片5、配置在电路基板7和半导体芯片5之间的密封树脂6。密封树脂6由本发明的半导体密封填充用树脂组合物的固化物形成，密封电路基板7和半导体芯片5之间的空隙。电路基板7具有内插板等基板以及设置在该基板的一个面上的配线4。电路基板7的配线4和半导体芯片5通过多个凸块3而被电连接。另外，电路基板7在与设有配线4的面相反侧的面上具有电极垫片2和设在电极垫片2上的焊锡球1，能够与其他电路部件连接。
电路基板7也可以是通常的电路基板，此外也可以是半导体芯片。在为电路基板的场合，可以使用以下基板：将玻璃环氧、聚酰亚胺、聚酯、陶瓷等绝缘基板表面形成有铜等金属层的不需要的部分蚀刻除去，形成配线图形的基板；通过镀铜等在绝缘基板表面形成配线图形的基板；在绝缘基板表面印刷导电性物质而形成配线图形的基板等。在配线图形的表面，也可以形成由低熔点焊锡、高熔点焊锡、锡、铟、金、镍、银、铜、钯等构成的金属层，该金属层可以仅由单一成分构成，也可以由多种成分构成。另外，也可以是多个金属层层叠而成的结构。
作为半导体芯片5，没有特别限定，可以使用硅、锗等元素半导体、砷化镓、磷化铟等化合物半导体等各种半导体。
凸块3是具有导电性的突起部。作为其材料，可以使用由低熔点焊锡、高熔点焊锡、锡、铟、金、银、铜等构成的材料，可以仅由单一成分构成，也可以由多种成分构成。另外，也可以形成层叠这些金属而成的结构的方式形成。作为应用特别广泛的凸块，可以举出焊锡凸块、铜凸块、在铜柱的前端形成有焊锡的凸块、金凸块等。另外，凸块可以在半导体芯片上形成，也可以在基板上形成，还可以在半导体芯片和基板两方上形成。
作为本发明的半导体装置，可以举出如图1所示的半导体封装体那样，在称为内插板的基板上搭载半导体芯片，并被树脂密封而成的装置，具体地，可以举出CSP(芯片尺寸封装体)或BGA(球栅阵列)等。另外，作为其他半导体封装体，可以举出通过在半导体芯片表面上将半导体芯片的电极部进行再配线，从而不使用内插板也能够搭载在基板上的封装体，具体可以举出被称为晶片级封装体的半导体封装体。作为搭载本发明的半导体封装体的基板，可以举出通常的电路基板，该基板是指与内插板相对、被称作母板的基板。
接着，关于本发明的半导体装置的制造方法的一个实施方式，基于使用形成有焊锡凸块的半导体芯片的一个例子，如下所示。
(1)供给环氧树脂组合物的第一工序
在环氧树脂组合物是糊状的情况下，使用分配器将其涂布在半导体芯片或基板的规定位置上。环氧树脂组合物的供给量根据半导体芯片的大小、凸块高度等来限定，适当设定为能够无间隙地填充半导体芯片和基板之间的空隙并且在倒装片连接时树脂在半导体芯片的侧壁传导而不附着于连接装置的量。
另外，使用膜状树脂组合物的情况下，通过加热加压、辊层压、真空层压等，粘附在半导体芯片或基板上。另外，膜状树脂组合物也可以粘附在半导体芯片上，在将膜状树脂组合物粘附在半导体晶片上后，进行切割，单片化为半导体芯片，从而可以制作粘附有膜状树脂组合物的半导体芯片。
(2)将半导体芯片和基板进行倒装片连接的第二工序
使用倒装片接合机等连接装置将半导体芯片和基板进行位置对准后，一边以焊锡凸块的熔点以上的温度对半导体芯片和基板进行加热，一边将其压合，将半导体芯片和基板连接，同时用熔融的环氧树脂组合物密封填充半导体芯片和基板之间的空隙。此时，通过本发明的环氧树脂组合物中所含的助熔剂，焊锡凸块表面的氧化膜被还原除去，焊锡凸块熔融，形成通过金属接合而成的连接部。
另外，也可以如下方式制造半导体装置：对半导体芯片和基板进行位置对准，在比焊锡凸块熔点低的温度下压合半导体芯片和基板来进行预固定后，通过用回流炉进行加热处理，使焊锡凸块熔融，将半导体芯片和基板连接，从而制成半导体装置。
进而，也可以如下方式连接半导体芯片和基板：对半导体芯片和基板进行位置对准，一边在焊锡凸块不熔融的温度且助熔剂的活性温度以上的温度下加热一边进行压合，从而排除半导体芯片的凸块和基板电极之间的树脂，将半导体芯片和基板之间的空隙密封填充，同时除去焊锡表面的氧化膜，之后，再次加热到焊锡熔点以上的温度，使焊锡熔融，连接半导体芯片和基板。再次加热到焊锡熔点以上的温度时，可以使用倒装片接合机，也可以用回流炉进行加热处理。
另外，所谓助熔剂的活性温度，是指开始表现出还原焊锡或锡等金属表面的氧化膜的效果的温度。在室温下是液态的助熔剂，如果在室温以上，则显示出活性。在室温下是固态的助熔剂，在其熔点或软化点以上的温度下成为了液态或低粘度状态时，由于在焊锡或锡等金属表面上均匀润湿且显示出活性，因此活性温度为熔点或软化点。
进而，为了提高连接可靠性，也可以用加热烘箱等对第二工序中得到的半导体装置进行加热处理，使环氧树脂组合物进一步固化。
实施例
以下，通过实施例和比较例来说明本发明，但本发明的范围不限于此。
(实施例1～5和比较例1～3)
基于表1所示的组成，在甲苯-乙酸乙酯溶剂中将各材料溶解混合，使得固体成分浓度为50～70％，制作清漆，使用刮刀涂布机将该清漆涂布在隔膜(PET膜)上后，在70℃的烘箱中干燥10分钟，从而制成厚度25～30μm的膜状树脂组合物。
表1
Figure BSA00000444007200131
原材料
苯氧树脂：ε-己内酯改性苯氧树脂PKCP80(Inchem Corporation制，产品名)
环氧树脂：三苯酚甲烷型多官能环氧树脂EP1032H60(日本环氧树脂公司制，产品名)
酸酐：3，4-二甲基-6-(2-甲基-1-丙烯基)-4-环己烯-1，2-二羧酸酐和1-异丙基-4-甲基双环-[2.2.2]辛-5-烯-2，3-二羧酸酐的混合物YH307(日本环氧树脂公司制，产品名)
助熔剂1：己二酸(西格玛奥德里奇公司制，产品名，熔点152℃)
助熔剂2：双酚酸(西格玛奥德里奇公司制，产品名，熔点167℃)
固化促进剂1：四(正丁基)鏻四氟硼酸盐PX-4FB(日本化学工业株式会社制，产品名)
固化促进剂2：正十六烷基三(正丁基)鏻四氟硼酸盐PX-416FB(日本化学工业株式会社制，产品名)
固化促进剂3：四(正丁基)鏻四苯基硼酸盐PX-4PB(日本化学工业株式会社制，产品名)
固化促进剂4：四苯基鏻四苯基硼酸盐TPP-K(北兴化学工业株式会社制，产品名)
固化促进剂5：三苯基膦TPP(北兴化学工业株式会社制，产品名)
固化促进剂6：2-苯基-4，5-二羟基甲基咪唑2PHZ(四国化成工业株式会社制，产品名)
填料：球状二氧化硅SE2050(Admatechs公司制，产品名)
膜状树脂组合物的评价
对于实施例1～5和比较例1～3中得到的膜状树脂组合物进行下述评价。结果示于表2。
(粘度测定)
粘度是基于平行板塑度计法，按照式(1)和式(2)，按照以下程序测定的。
准备如下样品：将冲切为直径6mm的圆形的膜状树脂组合物粘附在15mm见方(厚0.7mm)的玻璃板上，剥离隔膜后，配置为带有氧化膜的硅芯片(尺寸12mm见方，厚0.55mm)的氧化膜面与膜状树脂组合物接触。将该样品配置在倒装片接合机FCB3(松下生产科技公司制，产品名)上，在模头温度290℃、平台温度50℃、载荷14N、加压时间5秒(达到250℃)的条件下进行热压接。树脂体积假定为一定时，则式(2)的关系成立，因此用显微镜测定加压后的半径，按照式(1)算出250℃时的粘度。
η = 8 πFt Z 4 Z 0 4 3 V 2 ( Z 0 4 - Z 4 )
式(1)
η：粘度(Pa·s)
F：载荷(N)
t：加压时间(s)
Z：加压后的树脂厚度(m)
Z0：加压前的树脂厚度(m)
V：树脂的体积(m3)
Z/Z0＝(r0/r)2    式(2)
Z0：加压前的树脂厚度(m)
Z：加压后的树脂厚度(m)
r0：加压前的树脂半径(由于以直径6mm进行冲切，所以是3mm)
r：加压后的树脂半径
(储存稳定性)
将膜状树脂组合物放置在40℃的恒温槽中，以72小时后的250℃时的粘度为初期粘度的3倍以下的组合物为合格(○)，以大于3倍的组合物为不合格(×)，进行评价。这里，粘度测定是按照上述方法测定的。
(凝胶化时间的测定)
将剥离了隔膜的膜状树脂组合物配置在250℃的热板上，以直至变得不能用刮铲搅拌为止的时间为凝胶化时间。
(半导体芯片和基板的连接)
作为形成有在铜柱前端具有无铅焊锡层(Sn-3.5Ag：熔点221℃)的结构的凸块的半导体芯片，准备日立超LSI系统公司制造的JTEG PHASE11_80(尺寸7.3mm×7.3mm，凸块间距80μm，凸块数328，厚度0.55mm，产品名)；作为基板，准备表面具有通过预熔剂处理(pre-flux processing)而形成了防锈被膜的铜配线图形的玻璃环氧基板。接着，将膜状树脂组合物切出9mm×9mm，在80℃/0.5MPa/5秒的条件下粘附在基板上的搭载半导体芯片的区域，然后剥离隔膜。将粘附有膜状树脂组合物的基板吸附固定在倒装片接合机FCB3(松下生产科技公司制，产品名)的设定为40℃的平台上，使其与半导体芯片位置对准后，进行预固定工序，即在载荷25N、模头温度100℃的条件下进行5秒的压接(达到90℃)，将半导体芯片预固定在基板上。接着，作为第一工序，将倒装片接合机的模头温度设定为210℃，以载荷25N进行10秒的压接(达到180℃)。进而，作为第二工序，将倒装片接合机的模头温度设定为290℃，以载荷25N进行10秒的压接(达到250℃)，得到半导体芯片和基板连接了的半导体装置。
(导通检查)
对于半导体芯片和基板连接了的半导体装置，以可以确认328凸块的菊链(daisy-chain)连接的情况作为合格(○)，没能确认菊链连接的情况作为不合格(×)，进行评价。
(孔隙评价)
用超声波探伤装置(日立建机制FineSAT)对半导体芯片和基板连接了的半导体装置进行观察，以相对于芯片面积，孔隙所占面积为1％以下的作为合格(○)，以小于1％的作为不合格(×)，进行评价。
(连接状态评价)
通过断面研磨使半导体芯片和基板连接了的半导体装置的连接部露出，用光学显微镜进行观察。以在连接部没有看到捕获(trapping)、焊锡充分润湿配线的作为合格(○)，此外的作为不合格(×)，进行评价。
表2
Figure BSA00000444007200161
由表2的结果可知：在配合有作为叔磷化合物的三苯基膦的比较例1和配合有咪唑类的比较例2和3中，储存稳定性降低，与此相对，配合有季鏻盐的实施例1～5中，维持与比较例1～3同等的反应性的同时，可以实现良好的储存稳定性。另外，没有配合助熔剂的比较例3中，不能形成通过良好的金属接合而成的连接部，但配合有助熔剂的实施例1～5中，孔隙少，能够形成通过良好的金属接合而成的连接部。
如以上说明，通过使用本发明的半导体密封填充用环氧树脂组合物，不仅能够确保良好的储存稳定性，而且能够抑制孔隙并形成通过金属接合而成的连接部。

Claims (6)

1.一种半导体密封填充用环氧树脂组合物，以环氧树脂、酸酐、固化促进剂、助熔剂为必须成分，固化促进剂是季鏻盐。
2.根据权利要求1记载的半导体密封填充用环氧树脂组合物，其中，季鏻盐是四烷基鏻盐或四芳基鏻盐。
3.根据权利要求1或2记载的半导体密封填充用环氧树脂组合物，其中，进一步含有无机填料。
4.根据权利要求1～3中任一项记载的半导体密封填充用环氧树脂组合物，其形成为膜状。
5.一种半导体装置的制造方法，包括：
第一工序：将权利要求1～4中任一项记载的半导体密封填充用环氧树脂组合物供给到半导体芯片或基板上；
第二工序：对半导体芯片和基板进行位置对准后，对半导体芯片和基板进行倒装片连接，同时将半导体芯片和基板之间的空隙用所述半导体密封填充用环氧树脂组合物密封填充。
6.一种半导体装置，其具备：
基板；与该基板电连接的半导体芯片；密封所述基板和所述半导体芯片之间的空隙的密封树脂，该树脂由权利要求1～4中任一项记载的半导体密封填充用环氧树脂组合物的固化物形成。
CN2011100518708A 2010-03-16 2011-03-02 半导体密封填充用环氧树脂组合物、半导体装置及其制造方法 Pending CN102190864A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010059462A JP6045774B2 (ja) 2010-03-16 2010-03-16 半導体封止充てん用エポキシ樹脂組成物、半導体装置、及びその製造方法
JP2010-059462 2010-03-16

Publications (1)

Publication Number Publication Date
CN102190864A true CN102190864A (zh) 2011-09-21

Family

ID=44599793

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011100518708A Pending CN102190864A (zh) 2010-03-16 2011-03-02 半导体密封填充用环氧树脂组合物、半导体装置及其制造方法

Country Status (5)

Country Link
US (1) US20110241228A1 (zh)
JP (1) JP6045774B2 (zh)
KR (1) KR20110104430A (zh)
CN (1) CN102190864A (zh)
TW (2) TW201444884A (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103897344A (zh) * 2012-12-26 2014-07-02 第一毛织株式会社 用于封装半导体器件的环氧树脂组合物以及使用其封装的半导体器件
CN104137246A (zh) * 2012-02-24 2014-11-05 日立化成株式会社 半导体装置及其制造方法
CN104137240A (zh) * 2012-02-24 2014-11-05 日立化成株式会社 半导体用粘接剂、助熔剂、半导体装置的制造方法以及半导体装置
CN104185666A (zh) * 2012-02-24 2014-12-03 日立化成株式会社 半导体用粘接剂、助熔剂、半导体装置的制造方法以及半导体装置
US9425120B2 (en) 2012-02-24 2016-08-23 Hitachi Chemical Company, Ltd Semiconductor device and production method therefor
CN108779232A (zh) * 2016-02-25 2018-11-09 日立化成株式会社 环氧树脂成型材料、成型物、成型固化物以及成型固化物的制造方法
CN110223909A (zh) * 2019-05-29 2019-09-10 浙江荷清柔性电子技术有限公司 一种晶圆边缘处理方法及晶圆组件

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012089750A (ja) * 2010-10-21 2012-05-10 Hitachi Chem Co Ltd 半導体封止充てん用熱硬化性樹脂組成物及び半導体装置
TW201329145A (zh) 2011-11-28 2013-07-16 Nitto Denko Corp 底層充填材料及半導體裝置之製造方法
JP5813479B2 (ja) * 2011-11-28 2015-11-17 日東電工株式会社 シート状封止組成物及び半導体装置の製造方法
WO2013165323A2 (en) * 2012-04-05 2013-11-07 Mektec Manufacturing Corporation (Thailand) Ltd Method and encapsulant for flip-chip assembly
KR101867955B1 (ko) * 2012-04-13 2018-06-15 삼성전자주식회사 패키지 온 패키지 장치 및 이의 제조 방법
TWI600701B (zh) * 2012-07-19 2017-10-01 Nagase Chemtex Corp A semiconductor sealing epoxy resin composition and a method of manufacturing the semiconductor device
JP6102112B2 (ja) * 2012-07-30 2017-03-29 日立化成株式会社 エポキシ樹脂組成物及び電子部品装置
US9330993B2 (en) * 2012-12-20 2016-05-03 Intel Corporation Methods of promoting adhesion between underfill and conductive bumps and structures formed thereby
JP6587169B2 (ja) * 2013-05-13 2019-10-09 パナソニックＩｐマネジメント株式会社 光反射体用熱硬化性樹脂組成物
JP6280400B2 (ja) * 2014-03-07 2018-02-14 日東電工株式会社 アンダーフィル材、積層シート及び半導体装置の製造方法
KR101802583B1 (ko) 2015-06-23 2017-12-29 삼성에스디아이 주식회사 반도체 소자 밀봉용 에폭시 수지 조성물, 및 이를 사용하여 제조된 반도체 소자
JP2016006205A (ja) * 2015-09-16 2016-01-14 日東電工株式会社 シート状封止組成物及び半導体装置の製造方法
US9960137B1 (en) 2016-11-01 2018-05-01 Advanced Semiconductor Engineering, Inc. Semiconductor device package and method for forming the same
TWI717170B (zh) * 2019-12-26 2021-01-21 財團法人工業技術研究院 半導體裝置及其製作方法
CN113053833A (zh) * 2019-12-26 2021-06-29 财团法人工业技术研究院 一种半导体装置及其制作方法
WO2022079828A1 (ja) * 2020-10-14 2022-04-21 昭和電工マテリアルズ株式会社 組成物、樹脂組成物、及び複合体の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128746A (en) * 1990-09-27 1992-07-07 Motorola, Inc. Adhesive and encapsulant material with fluxing properties
US6180696B1 (en) * 1997-02-19 2001-01-30 Georgia Tech Research Corporation No-flow underfill of epoxy resin, anhydride, fluxing agent and surfactant
CN1656862A (zh) * 2002-05-23 2005-08-17 3M创新有限公司 纳米颗粒填充的底层填料
JP2009024099A (ja) * 2007-07-20 2009-02-05 Shin Etsu Chem Co Ltd 液状エポキシ樹脂組成物及び半導体装置

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3446731B2 (ja) * 2000-09-26 2003-09-16 松下電工株式会社 エポキシ樹脂組成物及び半導体装置
JP2002241469A (ja) * 2001-02-14 2002-08-28 Nitto Denko Corp 熱硬化性樹脂組成物および半導体装置
JP4753329B2 (ja) * 2001-02-14 2011-08-24 日東電工株式会社 熱硬化性樹脂組成物および半導体装置
JP3871032B2 (ja) * 2001-12-25 2007-01-24 信越化学工業株式会社 液状エポキシ樹脂組成物及びフリップチップ型半導体装置
US7166491B2 (en) * 2003-06-11 2007-01-23 Fry's Metals, Inc. Thermoplastic fluxing underfill composition and method
JP4655501B2 (ja) * 2004-04-12 2011-03-23 日立化成工業株式会社 液状封止樹脂組成物ならびに電子部品装置およびその製造方法
JP5082445B2 (ja) * 2004-09-29 2012-11-28 日産化学工業株式会社 変性エポキシ樹脂組成物
JP2006265484A (ja) * 2005-03-25 2006-10-05 Fujitsu Ltd 接着性樹脂組成物及び電子装置
JP5388430B2 (ja) * 2007-07-24 2014-01-15 サンスター技研株式会社 アンダーフィル材
JP5493327B2 (ja) * 2007-12-18 2014-05-14 日立化成株式会社 封止充てん用樹脂組成物、並びに半導体装置及びその製造方法
JP5581576B2 (ja) * 2008-04-02 2014-09-03 日立化成株式会社 フラックス活性剤、接着剤樹脂組成物、接着ペースト、接着フィルム、半導体装置の製造方法、及び半導体装置
JP5599561B2 (ja) * 2008-07-22 2014-10-01 日立化成株式会社 熱硬化性樹脂組成物、これを用いた光半導体素子搭載用基板及びその製造方法並びに光半導体装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128746A (en) * 1990-09-27 1992-07-07 Motorola, Inc. Adhesive and encapsulant material with fluxing properties
US6180696B1 (en) * 1997-02-19 2001-01-30 Georgia Tech Research Corporation No-flow underfill of epoxy resin, anhydride, fluxing agent and surfactant
CN1656862A (zh) * 2002-05-23 2005-08-17 3M创新有限公司 纳米颗粒填充的底层填料
JP2009024099A (ja) * 2007-07-20 2009-02-05 Shin Etsu Chem Co Ltd 液状エポキシ樹脂組成物及び半導体装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
司小燕等: ""环氧树脂胶粘剂增韧改性的研究进展"", 《粘接》 *
张凯等: "环氧树脂改性技术研究进展", 《化学推进剂与高分子材料》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104137246A (zh) * 2012-02-24 2014-11-05 日立化成株式会社 半导体装置及其制造方法
CN104137240A (zh) * 2012-02-24 2014-11-05 日立化成株式会社 半导体用粘接剂、助熔剂、半导体装置的制造方法以及半导体装置
CN104185666A (zh) * 2012-02-24 2014-12-03 日立化成株式会社 半导体用粘接剂、助熔剂、半导体装置的制造方法以及半导体装置
US9425120B2 (en) 2012-02-24 2016-08-23 Hitachi Chemical Company, Ltd Semiconductor device and production method therefor
US9803111B2 (en) 2012-02-24 2017-10-31 Hitachi Chemical Company, Ltd. Adhesive for semiconductor, fluxing agent, manufacturing method for semiconductor device, and semiconductor device
CN110556344A (zh) * 2012-02-24 2019-12-10 日立化成株式会社 半导体用粘接剂、半导体装置的制造方法以及半导体装置
CN103897344A (zh) * 2012-12-26 2014-07-02 第一毛织株式会社 用于封装半导体器件的环氧树脂组合物以及使用其封装的半导体器件
US9695294B2 (en) 2012-12-26 2017-07-04 Cheil Industries, Inc. Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same
CN108779232A (zh) * 2016-02-25 2018-11-09 日立化成株式会社 环氧树脂成型材料、成型物、成型固化物以及成型固化物的制造方法
CN110223909A (zh) * 2019-05-29 2019-09-10 浙江荷清柔性电子技术有限公司 一种晶圆边缘处理方法及晶圆组件
CN110223909B (zh) * 2019-05-29 2024-03-26 浙江荷清柔性电子技术有限公司 一种晶圆边缘处理方法及晶圆组件

Also Published As

Publication number Publication date
KR20110104430A (ko) 2011-09-22
TW201444884A (zh) 2014-12-01
JP6045774B2 (ja) 2016-12-14
US20110241228A1 (en) 2011-10-06
TW201144348A (en) 2011-12-16
JP2011190395A (ja) 2011-09-29

Similar Documents

Publication Publication Date Title
CN102190864A (zh) 半导体密封填充用环氧树脂组合物、半导体装置及其制造方法
CN102453340B (zh) 半导体密封填充用热固性树脂组合物以及半导体装置
JP2011231137A (ja) 半導体封止充てん用エポキシ樹脂組成物及び半導体装置
CN102057475B (zh) 半导体装置的制造方法以及半导体装置
TWI603439B (zh) 底部塡充組合物及半導體器件及其製造方法
CN103249559B (zh) 半导体密封填充用膜状树脂组合物、半导体装置的制造方法和半导体装置
JP5957794B2 (ja) 積層シート及び半導体装置の製造方法
JP2015131969A (ja) 半導体封止充てん用エポキシ樹脂組成物
JP2011014717A (ja) 接着フィルム、多層回路基板、電子部品及び半導体装置
JP2012158719A (ja) 半導体封止充てん用エポキシ樹脂組成物並びにそれを用いた半導体装置及び半導体装置の製造方法
JP2012238699A (ja) 半導体装置の製造方法、半導体素子付き半導体ウェハの製造方法及び接着剤層付き半導体ウェハの製造方法
JP5978725B2 (ja) 半導体装置の製造方法
JP6225963B2 (ja) 液状感光性接着剤
CN102257064A (zh) 液体树脂组合物和半导体器件
JP5891605B2 (ja) 半導体装置の製造方法、及び半導体ウェハ積層体の製造方法
JP6399152B2 (ja) 液状感光性接着剤、接着剤層付き半導体ウェハの製造方法、半導体装置の製造方法及び半導体素子付き半導体ウェハの製造方法
JP5685030B2 (ja) 電子部品用接着剤
JP6132056B2 (ja) 半導体装置の製造方法
US20210292616A1 (en) Adhesive composition for semiconductor circuit connection and adhesive film containing the same
JP2005298677A (ja) 液状封止樹脂組成物ならびに電子部品装置およびその製造方法
JP2012089619A (ja) 半導体装置の製造方法、及び該製造方法を用いて製作された半導体装置

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20110921