TWI243082B - Electronic device - Google Patents
Electronic device Download PDFInfo
- Publication number
- TWI243082B TWI243082B TW091107878A TW91107878A TWI243082B TW I243082 B TWI243082 B TW I243082B TW 091107878 A TW091107878 A TW 091107878A TW 91107878 A TW91107878 A TW 91107878A TW I243082 B TWI243082 B TW I243082B
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- Taiwan
- Prior art keywords
- flux
- metal
- compound
- electrode
- substrate
- Prior art date
Links
- 239000002184 metal Substances 0.000 claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 claims abstract description 107
- 239000000758 substrate Substances 0.000 claims abstract description 74
- 229910000679 solder Inorganic materials 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 230000004907 flux Effects 0.000 claims description 90
- 229910000765 intermetallic Inorganic materials 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 25
- 239000010931 gold Substances 0.000 claims description 21
- 239000003973 paint Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 9
- 239000012792 core layer Substances 0.000 claims description 8
- 230000002079 cooperative effect Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910017980 Ag—Sn Inorganic materials 0.000 claims description 4
- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 4
- -1 Cu-Sn compound Chemical class 0.000 claims description 4
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910015363 Au—Sn Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 2
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 2
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 41
- 229910052738 indium Inorganic materials 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 52
- 239000000463 material Substances 0.000 description 30
- 238000002844 melting Methods 0.000 description 27
- 230000008018 melting Effects 0.000 description 27
- 239000004065 semiconductor Substances 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 230000017525 heat dissipation Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 229910017944 Ag—Cu Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011295 pitch Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910001374 Invar Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910018100 Ni-Sn Inorganic materials 0.000 description 1
- 229910018532 Ni—Sn Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- 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
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/4853—Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3485—Applying solder paste, slurry or powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
- H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/341—Surface mounted components
- H05K3/3431—Leadless components
- H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/0554—External layer
- H01L2224/05599—Material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/11—Manufacturing methods
- H01L2224/11001—Involving a temporary auxiliary member not forming part of the manufacturing apparatus, e.g. removable or sacrificial coating, film or substrate
- H01L2224/11003—Involving a temporary auxiliary member not forming part of the manufacturing apparatus, e.g. removable or sacrificial coating, film or substrate for holding or transferring the bump preform
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/16235—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the bump connector connecting to a via metallisation of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—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
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—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
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Description
1243082 A7 _ B7 五、發明説明(> 本發明係有關於一種焊劑,使用焊劑之連接方法或電 子機器。 在S η - P b系焊劑中,除了已經被廣泛應用在電子 機器之製造上,且熔點爲1 8 3 °C的6 3重量% S η -3 7重量% P b的共晶焊劑(以下如S η - 3 7 P b般元 素的比例以去掉重量%來表示,而沒有記載組成比例的元 素則爲剩下來的重量% )以外,高溫系焊劑一般已知有被 稱爲高鉛焊劑的高P b的P b - 5 S η (熔點:3 1 0〜 3 1 4 °C ) ,Pb — 10Sn (熔點:275 〜302 °C )等。這些則被加熱到3 3 0 t附近來使用,之後,則不 讓該焊接部熔化,而可以進行以熔點低的S η - 3 7 P b 來連接的溫度階層連接。該溫度階層連接適用於用於接合 (die bond)晶片的半導體裝置、或將晶片作覆晶(flip chip )連接的 B G A ( Ball Grid Array ) 、C S P ( Chip
Scale Package)等。特別是當將晶片作覆晶連接時,一般是 藉由一被稱爲 C 4 (Controlled Collapse Chip Connection )連接之將焊劑突點(bump )使用於電子零件的電極與基 板的電極之間的方式來進行。 又,高鉛焊劑,則除了由於熔點的關係而可以達成與 S η - 3 7 P b的溫度階層連接外,由於含有許多軟質的 鉛,因此有整個焊劑柔軟的性質。而此特別是在如與晶片 的連接部般之會因爲與基板的熱膨脹係數差而導致發生機 械上的應力等的位置,必須具備在連接部能夠緩和應力的 特性使然,因此適合使用柔軟的焊劑,而使用該軟質的高 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 4 _ (請先閲讀背面之注意事項再填寫本頁) C· 、11 經濟部智慧財產局員工消費合作社印製 1243082 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明( 錯焊劑,可以進行直接將矽晶片焊接在基板的覆晶(fHP chip )連接。 但是由於考慮到環境因素,乃逐漸開發出已經從焊劑 中排除錯的無錯焊劑材料,以及使用其之焊接方法。 用來替代Sn-37Pb的無錯焊劑材料則已經有系、 Sn-Ag-Cu系、Sn-Cii系、Sn-Zri系以及在該些添加了 Bl或 In而達成低熔點化的焊劑材料。另一方面,高溫系之高鉛焊 劑的替代材料,雖然最有可能的焊劑材料有Sn_5Sb(熔點: 2 3 2〜2 4 0 °C ),但若是考慮到在回焊(reflow)爐內之 基板內的溫度變動等因素時,則要是不讓由Sn_5Sb所構成的 連接部熔化,則很難使用上述之無Pb焊劑材料來進行溫度階 層連fe:。此外,雖然已知到有A u - 2 0 S η (熔點:2 8〇°C ),但由於 該材料硬,且成本高,因此其用途被限制。特別是針對於在不 同熱膨脹係數之材料間的連接,例如Si晶片與基板間的連接 、或是與大型的Si晶片的連接,由於焊劑硬,且緩和應力的 可能性低,因此會有破壞到S i晶片的顧慮而無法被使用。在 此,如最近之特開平1 1 - 1 72352號所述,乃提出一 Zn_A1系焊 劑,而含有Ge、Mg等的材料。該材料的熔點爲2 8 0 t:〜 3 8 0 °C,雖然其熔點適合作爲高溫焊劑的替代材料,但由 於焊劑本身硬、或含有許多反應性高的Zn、A1,因此擔心會 帶來腐鈾等影響。 因此,本發明的目的在於提供一種在電子零件內可以 當作電極來使用之含有許多鉛且熔點高之焊劑的替代材料 及使用其之連接方法以及電子機器。特別是提供一種使用 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)
1243082 Α7 Β7 五、發明説明(3 在稱爲C 4連接之桶(barrel )狀之電極等的無鉛材料、以 及使用其之連接方法。 在本發明中爲了要解決上述課題,乃將以往使用高鉛焊 劑之電子零件的電極與基板之電極間之連接部設定如下。 首先,將單體金屬、合金、化合物或含有該些混合物 的金屬球(ball )設爲以S η、或I η之其中一者的焊劑與 和該金屬球的反應所產生之金屬間化合物來連結及/或以 該焊劑與該金屬間化合物兩方來連結之構造的連接部。在 本說明書中所謂的金屬球或金屬球相則意味著具有球狀或 粒子形狀,且至少表面或是外層(亦即,被覆部分)爲金 屬及/或作爲金屬間化合物的球或粒子,亦即,金屬球或 金屬球相的芯部,則除了金屬外,也將爲塑膠或是無機物 等,且表面或是外層爲金屬及/或金屬間化合物所被覆者 定義作爲金屬球(ball)。 又,將單體金屬、合金、化合物或含有該些混合物的 金屬球設爲以S η - C u系焊劑,S η - A g系焊劑、 S η - A g — C u系焊劑,在該些添加了 I η、Ζ η、 Β 1之其中一個以上的焊劑中的一種以上的焊劑與和該金 屬球的反應所產生的金屬間化合物來連結及/或以該焊劑 與該金屬間化合物兩者來連結的構造。 連接方法則如下所述。 將由單體金屬、合金、化合物或含有該些混合物的金 屬球、與含有S η或I η之其中一者的焊劑球混合而成的 塗料供給到電子零件的電極與基板的電極之間,且將該些 本紙張尺度適用中國國家標準(CNS ) Α4規格(210 X 297公釐) (請先閲讀背面之注意事項再填寫本頁} •-^衣· 訂 經濟部智慧財產局員工消費合作社印製 1243082 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(4 加熱讓該焊劑球部分熔化,而以該焊劑與由和該金屬球的 反應而產生的金屬間化合物及/或以該焊劑與該金屬間化 合物兩者來連結該金屬球之間,該金屬球與該電子零件之 電極之間、以及該金屬球與該基板之電極之間。 又,將由單體金屬、合金、化合物或含有該些混合物 的金屬球、與含有Sn-Cu系焊劑、Sn-Ag系焊劑、Sn-Ag-Cu 系焊劑,在該些添加了 In、Zn、Bi之其中一個以上的焊劑中 的一種以上混合而成的塗料供給到電子零件的電極與基板 的電極之間,且將該些加熱讓該焊劑球部分熔化,而以該 焊劑與由和該金屬球的反應而產生的金屬間化合物及/或 以該焊劑與該金屬間化合物兩者來連結該金屬球之間,該 金屬球與該電子零件之電極之間、以及該金屬球與該基板 之電極之間。 在此,上述金屬球爲Cu、Ag、Au、Al、Ni、Cu合金、 C u - S n化合物、A g - S n化合物、A u - S n化合物、A1 - A g化合物 、Zn-Al化合物、或含有該些混合物的球。又,在上述金屬 球表面實施鍍A1、或鍍Ag或鍍Sn的單體金屬、或鍍含有 S η的合金、或是2層電鍍、下層爲鍍Ni,而在其表面則 鍍Au、或是下層鍍Ni ,而在其表面鍍Ag之其中一者 〇 電極的形狀爲桶狀、圓柱狀、直方體、腰(wais)狀。 又,將如上所製作的電子機器利用無鉛焊劑而連接到 其他的基板。 又,在如上所製作的電子機器所使用的基板則使用具 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -7- 1243082 A7 B7 五、發明説明()5 有金屬芯(metalcore )層的基板。 (請先閲讀背面之注意事項再填寫本頁) 本發明之其他目的、特徵、以及優點則可以由與所附 圖面相關之以下本發明之實施例的記載可知。 請參照圖面來說明本發明之無鉛材料、電子機器、以 及連接方法。 (實施形態1 ) 圖1爲實施本發明之電子機器的例子。該安裝構造體 1 9係將已作覆晶(flipchip )連接有半導體晶片的中間基 板2則被安裝在印刷配線基板1 5。圖2係表該半導體晶 片1與中間基板2之間之連接部的斷面。半導體晶片1的 電極3與中間基板2之電極4間之根據覆晶的連接部5, 則互相已分離的金屬球相6乃被分散而該金屬球相6之間 則藉由焊劑相7、以及由焊劑與該金屬球的反應所產生的 金屬間化合物相8所連結。 連接部的形狀在圖1雖然是桶狀,但也可以是如圖3 (a)所示般爲直方體或圓柱狀,圖3 (b)所示之中央 經濟部智慧財產局員工消費合作社印製 變細的腰形。又,除該此之外,雖然未圖示,但是也可以 是梯形。在圖3 ( a )所示之直方體、圓柱狀的連接中, 則藉著將連接部的厚度變薄,可以在高度方向提高安裝密 度。因此,利用該圖2之形狀的L G A ( Land GHd Array )連接,則可以適用於不只是小型化,連薄型化也非常重 要的行動電話、數位攝影機、筆記型電腦、P D A ( Personal Digital Assistant)等之攜帶用電子機器的安裝上。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -8 - 1243082 A 7 _ B7___
五、發明説明()B 在_ 3 ( b )所示的腰形中,可以減低在連接端部所產生 (請先閲讀背面之注意事項再填寫本頁) 的應力,又,藉著加長電極3與電極4之間的距離可以延 長壽命。因此,圖3 ( b )之腰形的連接適合於製品的壽 命非常重要之大型的電腦、汽車用的電子機器等。在圖2 至圖4所示之任一形狀中,爲了要更加提升連接部的壽命 ,則讓因爲半導體晶片1 、中間基板2的熱膨脹係數的差 所產生的應力分散會極爲有效。又,可以將樹脂封入到半 導體晶片1與中間基板2之間。而從半導體晶片1之上以 樹脂作上面被覆(top coat)會很有效果。又,爲了要讓在 半導體晶片1所產生的熱得以散熱,則可以在半導體晶片 1上安裝散熱片等。 經濟部智慧財產局員工消費合作社印製 在圖2的例子中,金屬球相6爲C u、焊劑相7爲 S η,而由金屬球與焊劑的反應所產生的金屬間化合物相 則由C u - S η金屬間化合物所構成。請參照圖4、圖5 來說明該圖1所示之安裝構造體1 9的製造方法。在第1 過程中則藉由印刷將混合塗料9供給到中間基板2的電極 4,在第2過程中則搭載半導體晶片1。將此時之混合塗 料9的供給狀態放大表示在圖6,而混合塗料9則使用助 熔劑成分爲由C u所構成的金屬球6、與由S η所構成的 焊劑球1 0而混合而成。在第3過程中則將該些實施回焊 (veflow )加熱而得到連接部5。在第4過程中則藉著密封 樹脂1 2來密封晶片周圍。在第5過程中,則將焊劑球 1 4供給到與已安裝了半導體晶片1的面呈相反側的中間 基板2的電極1 3,在第6過程中,在印刷配線基板1 5 -9 - 本紙張尺度逍用中國國家標準(CNS ) A4規格(210X297公釐) 1243082 A7 B7 五、發明説明(y (請先閲讀背面之注意事項再填寫本頁) 的配線突部(land )設置迎面焊劑1 7,而在第7過程中, 則對該些實施回焊加熱而將焊劑球1 4與迎面焊劑1 7以 連接部1 8來連接,而得到安裝構造體1 9。 經濟部智慧財產局員工消費合作社印製 在第3過程的加熱溫度則必須是一要讓焊劑球1 〇的 S η熔化的溫度,雖然是依據焊劑球1 〇的大小而定,但 最好是在S η的熔點2 3 2 °C以上。但是加熱後,爲了要 將連接部以較該連接部形成時的溫度爲高的溫度來維持連 接狀態,乃在遠較於S η的熔點爲高的溫度,亦即,最高 溫度2 8 0 °C下實施回焊。塗料的助熔劑成分1 1則必須 S η會熔化,而能夠確保住與C u的沾溼性,而可以是 R M A ( Rosin Mildly activated) 、R A ( Rosin Activated )之任一者,而此次是採用松香(Rosin)系的RMA型式 。環境雖然最好是在大氣環境中,但爲了要更加提升C u 與S η之間的沾溼性,則是在氮氣等之惰性氣體環境中進 行。R Μ Α型式則適合於難以洗淨的安裝構造,例如間距 非常狹窄的構造、或是即使是淸洗,其洗淨殘渣反而會造 成問題的構造。此時,由於活性弱,因此最好是在氮氣等 的惰性氣體環境下來進行連接。R Μ A型式最好是一可以 洗淨的構造。此時,則在大氣環境中也可以進行連接。又 ,也可以使用一在連接後可以當作塡平劑(underfill )來 利用的助熔劑。該塡平劑(underfill )則將半導體晶片1與 中間基板2之間全部覆蓋,但也可以如圖7所示’即使只 以樹脂2 0來覆蓋電極的周圍,由於可以緩和連接端部的 應力集大情形,因此可以有效地提高連接部的壽命。 -10- 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) 1243082 A7 _B7____
五、發明説明()B (請先閲讀背面之注意事項再填寫本頁) 若將如圖6所構成者加熱時,則焊劑球1 0的S η會 熔化,而在與金屬球6的C u之間的界面形式金屬間化合 物,而將C u的焊劑球相6彼此加以連接。此時之連接部 5由金屬顯微鏡的觀察結果則表示在圖8,其模型圖則表 示在圖9。在界面則形成有C u與S η的金屬間化合物8 的層。又,已熔化的S η,由於半導體晶片1的電極3、 中間基板2的電極4均形成金屬間化合物,因此,C u的 金屬球相6與電極3、電極4分別被連接。藉由形成該些 的化合物層,即使是在2 5 0 °C以上的高溫下也能夠維持 強度。最後圖1中的連接部5 ,則焊劑球1 0的S η的一 部分成爲C u - S η金屬間化合物(C u 5 S η 5、熔點 約6 3 0 °C ),而接觸部以及其附近則成爲高熔點化。例 如即使剩下來的S η熔化,然其他的部分未熔化,則也可 以充分地確保耐得住在之後焊接時之製程的強度。 經濟部智慧財產局員工消費合作社印製 又,在零件與基板之間所產生的應力,由於C u是軟 的,因此在殘留在連接部內的C u內會有某種程度的變形 ,而對於使用高鉛焊劑的連接部可以利用該方式來代替。 因此若是考慮到在焊接後之接合部的耐熱疲勞性時,則當 互相分離的C u的金屬球6間的距離極短時,則即使接觸 部已經金屬間化合物化,由於在通常的金屬球之間容易變 形,因此希望S η或C u殘留下來。亦即,在最終的連接 部5內,由於硬的化合物的比例小’而容易變形的c u的 金屬球相6的比例大者的耐熱疲勞性會變好,因此’藉著 調整所要熔化的S η量、熔化時間以及熔化時間中的至少 -11 - 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) 1243082 A7 B7 五、發明説明(》 其中一者,可設成C u的金屬球彼此接觸的狀態,而最好 是藉由金屬間化合物來連結金屬間化合物彼此。 (請先閲讀背面之注意事項再填寫本頁) 因此,對於具有如圖2所示之連接部的電子機器,在 以後的過程中可以進行以徑利用S η - P b系焊劑所進行 的溫度階層連接,由於該接合部在2 5 0 °C左右的焊接溫 度下不會熔化,且能夠保持接合,因此在之後安裝到電路 基板時,接合部不致於發生剝離。在此,利用該S η -P b系焊劑所進行的後過程,若是考慮到環境,則換成 S π — Cu 系、Sn — Ag 系、Sn — A g — Cu 系、 3 11-(:11系、3 11-2 11系、以及在該些添加了:6 1或 I η以達成降低熔點的無鉛焊劑材料,而對其他的基板作 溫度階層連接。 經濟部智慧財產局員工消費合作社印製 此外,在此,雖然在圖1中金屬球6使用C u,但並 不限於此,也可以使用Ag、Au、Al 、Ni 、Cu合 金、Cu — Sn化合物、Ag — Sn化合物、Au — Sn 化合物、A 1 - A g化合物、Ζ η - A 1化合物。由於 A u的沾溼性良好,因此可以有效地減少連接部的孔洞( void )。又,由於A u本身是軟的,因此適合於緩和應力。 又,A 1除了其金屬本身是軟的,而適合於緩和應力外, 其成本也較A u爲便宜。 又,在該金屬球6的表面則實施鍍A u、或鍍A g、 或鍍S η的單體金屬、或是鍍含有s η的合金、或2層電 鍍,下層鍍N i ,在其表面則鍍A u、或是下層鍍N i , 而在其表面則鍍A g的其中任一者,而能夠提高沾溼性以 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 12 - 1243082 A7 B7 五、發明説明(>〇 (請先閱讀背面之注意事項再填寫本頁) 及提高強度。鍍2層的優點則在於保存安定性良好。當會g 夠提高沾溼性時,則可以有效地減少在連接部內的孔洞。 又,藉由電鍍處理,已熔化的焊劑容易沿著金屬球6而沾 溼擴散,而能夠將金屬球6之間配置在更均勻的間隔。又 ,將B i等1重量%以上微量地添加在S η,而能夠提升 焊劑的流動性,具有可提升到端子上的沾溼性,但是若 B i在5重量%以上時,由於會很脆,因此並不好。 爲了要減低整個連接部5的熱膨脹,金屬球6除此外 ,也使用不脹鋼系(invar )系氧化砂、氧化銘、A 1 N、 S i C等,在表面讓焊劑沾溼的金屬化物、或鍍S η、 I η等、或實施焊劑電鍍利用均勻分散的混合塗料9。 經濟部智慧財產局員工消費合作社印製 又,對於在連接部產生大的應力的組合,也可以更追 加混合塑膠球或是單獨來使用。該塑膠球素材可以利用聚 醯亞胺系、耐熱環氧系、矽氧系、各種聚合物粒子( polymer beads )或是由該些變性而成者,而使用將表面已實 施焊劑沾濕之金屬化的塑膠球與其他的金屬球混合、或是 單獨讓其均勻分散的混合塗料9,而能夠減低連接部5的 剛性。 金屬球6不一定要是球狀,也可以是在表面有嚴重凹 凸者、混合有棒狀、樹枝狀、角狀等者。而爲球狀的優點 即在於印刷性,在連接狹窄間距時,則最好是使用球狀者 。樹枝狀晶等的優點即在於鄰接之樹枝狀晶的接觸部多( 藉由C u彼此之互相纏繞的化合物接合多),即使金屬量 相對較少,在高溫時也能夠確保強度,而能夠期待提升耐 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -13- 1243082 A7 B7 五、發明説明(>1 (請先閲讀背面之注意事項再填寫本頁) 熱疲勞性。因此,最後樹脂狀晶會因爲接觸而繫在一起, 而能夠作彈性的運動,而可說是非常理想。因此會有若是 以S η等暫時包住C u的樹枝狀晶而球形化,而將其與塗 料成分混合而可以當作混合塗料來使用的方法。 在圖2的例子中,焊劑球1 0雖然是使用S η,但除 此外也可以使用S η - C u系焊劑、S η - A g系焊劑、 Sn—Ag—Cu系焊劑。當Cu進入到Sn中時,除了 會造成熔點降低外,當爲C u所構成的金屬球6時,則可 以抑制C u從金屬球6熔出。又,A g也有降低熔點的效 果。當使用在該些添加了 I η、Zn、B i之其中一種以 上的焊劑中的一種以上時,則更會使熔點降低,而能夠更 加降低在圖4之第3過程中的連接溫度。又即使是S η系 以外,也可以使用I η以降低連接溫度。 經濟部智慧財產局員工消費合作社印製 在混合塗料9中的金屬球6與焊劑球1 0的大小,由 於當太過微細時,其沾溼性會變性,因此特別希望焊劑是 在1 // m以上。由於上限値最終是要使電極成爲一具有1 個金屬球之圖1 0所示的構造,因此係根據電極形狀來決 定。該構造由於金屬球單體占了連接部的許多部分,因此 當爲使用C u的金屬球時,由於熱傳導性非常優良,因此 能夠期待散熱特性。 雖然回焊是在最高溫度爲2 8 0 °C下來進行,但是當 焊劑球1 0的S η殘留許多時,則藉由更加提高連接溫度 ,而使金屬間化合物的量相對地變多即可以解決。又,在 連接後,則設置蝕刻過程讓金屬間化合物成長,而能夠減 -14- 本紙張尺度適用中國國家標準(CNS ) Α4規格(210'乂297公釐) 1243082 Μ Β7 五、發明説明()12 (請先閲讀背面之注意事項再填寫本頁) 少S η量。此外,當在高溫下太過於長時間蝕刻時,則 C u 3 S η化合物會在C u側成長,由於c u 3 S η的機 械上性質是硬且脆,因此最好要抑制不要讓它成長以確保 強度。若是可以儘可能地提高連接溫度,則不需要蝕刻之 後續過程。 不管是何者,本實施例的連接方法,由於可以使連接 溫度較以往的高鉛焊劑爲降低(低溫化),因此能夠減低 熱對於半導體晶片1、中間基板2所造成的損傷。半導體 晶片1則除了 S i晶片,由G a A s所構成的晶片外,也 可以是CSP、BGA等。又,中間基板2 —般雖然是使 用玻璃環氧等的有機基板,但是當要高密度安裝時,則必 須要使用內建(bulidup)基板等。又,當爲汽車等要求高 耐熱的電子機器時,則可以使用陶瓷基板。又當必須要通 過基板來散熱時,則適合使用金屬芯(metal core )基板。 (實施例2 ) 經濟部智慧財產局員工消費合作社印製 在實施例1中,混合塗料9的供給以及連接,雖然是 藉由印刷在中間基板2上實施回焊來進行,但是以下則說 明其他的方法。 一般如被稱爲 WL — CSP ( Wafer Level Chip Size Package )般,乃採用事先在晶圓4 0狀態之各晶片4 1的 電極上形成突部(bump )的方法。該製造過程則表示在圖 1 1。首先,利用濺射器或是蝕刻,而在S i等的晶圓 40上形成A1 、A1— Cu合金等的電極墊42,更者 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -15 - 1243082 A7 B7 五、發明説明()13 ,在第2過程中,在藉由矽氧化膜全面地被覆表面保護膜 (請先閱讀背面之注意事項再填寫本頁) 4 3後,則在電極墊4 2上形成開口部。在接下來的第3 過程中,將光阻劑4 4供給到必要的位置,在第4過程中 則形成由C r/C u/N i或C r/C u/A u等所構成 的金屬多層膜4 5,在第5過程中則更將表面保護膜4 6 形成在必要的位置,而得到被再配線的電極墊4 7。爲了 要提高沾溼性,可以在該電極墊4 7上形成A u等的層。 將混合塗料9藉由印刷而供給到該電極墊4 7上,在第 6過程中則藉由加熱而得到突部(bump ) 4 8。之後,在 第7過程中則切割成各晶片4 1的大小,而得到附設突部 的S i晶片4 9。將該晶片4 9以面朝下的方式搭載在中 間基板上,而藉由回桿(reflow )加熱、或加壓•加熱方式 來連接。 經濟部智慧財產局員工消費合作社印製 除了如上述實施例般以放入助熔劑之具有粘著性的塗 料來印刷外,也可以藉由分配器來供給該混合塗料9。在 將混合塗料供給到1 0 0 // m晶片之高密度的電極時,若 將電極直徑大約設爲5 0 // m時,則金屬球6、焊劑球 1 0的直徑或是尺寸最好是爲電極直徑之1/1 〇左右的 5 //m左右。因此,若是一已混合有3〜8 //m的直徑或 尺寸的C u之焊劑球的塗料時,則粒徑相對於突部(bump )直徑則不會明顯。C u即使是混入微細粒子,雖然也可 以藉由松香(rosin )來還原,但由於微細粒子的S η球很 難藉由松香來還原,但可以當作含有些微之鹵素等之活性 劑的R Μ Α型式的助熔劑來使用。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 16 _ 1243082 A7 B7 五、發明説明(》4 又,也可以事先在其他的場所將該些的混合塗料9加 熱而成爲球狀,而將成爲該金屬球與焊劑之集合體的球個 別地供給到電極上。該過程則表不在圖1 2。利用掩罩( mask ) 5 1將混合塗料9印刷於在第1過程中未被焊劑沾 溼的基材5 0上,在第2過程中實施加熱而得到混合塗料 的集合體的球5 2 (第3過程)。利用振動送料治具5 3 等將此在第4過程中供給到半導體晶片1的電極3上,藉 由對其加熱可以得到附設突部5 4的半導體晶片5 5 (第 5過程)。將此在第6過程中搭載在已實施可連接突部 5 4的表面處理5 6,例如迎面焊劑、或鍍A u等的中間 基板2上,在第7過程中實施加熱,在第8過程中藉由樹 脂來密封5 7而得到安裝構造體5 8。 又,在由C u等所構成之金屬之細線的表面實施S η 等的焊劑鍍敷,將其加以細切,而取代金屬球6、焊劑球 1 0而塗料化,而可藉由印刷、分配器等來供給。又,在 C u箔的表面實施鍍S η等,而個別供給由沖壓而形成爲 圓盤狀者、或是加以塗料化。 在基板的電極,則爲了要提高沾淫性,則也可以實施 鍍Sn、鍍Sn合金、鍍Au、鍍Ag等的處理。又,在 基板的電極也可以印刷混合塗料、或是藉由分配器等而供 給混合塗料。將由使用了 S η、S η合金的焊劑所構成的 焊劑供給到基板上的電極,對於提高沾溼性極爲有效。 (實施例3 ) (請先閲讀背面之注意事項再填寫本頁) C· 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) -17- 1243082 A7 _ B7_ 五、發明説明()15 (請先閲讀背面之注意事項再填寫本頁) 虽在惰性境中將微細粒、或是樹枝狀晶的C u粉, 具有大約等效直徑的S η焊劑加以混合,而在室溫下實施 壓縮成形時,則可以得到不占空間的複合焊劑。而可將其 加工成圓板狀、角狀。在該狀態下,由於未讓作爲焊劑球 的s η熔化,因此,C U與S η處於未反應狀態,在焊接 時,在S η會熔化的2 3 2 °C以上會成爲可自由運動的狀 態。又,讓該些粒子均勻地分散而載置在事先與端子間距 配合的金屬掩罩(metal mask)上,而能夠定位在S i晶片 的端子上而加以供給。又,也可以將表面已實施爲S η所 沾溼之表面處理之低膨脹的石英、不脹鋼(invar )等均勻 地分散。 經濟部智慧財產局員工消費合作社印製 又,爲了要更加的柔軟,同樣地也可以讓已實施表面 同樣爲S η所沾溼之表面處理的約1 // m的耐熱性的共聚 物粒子等均勻地分散。該共聚物粒子等的橡膠效果可以提 高耐衝擊性、耐溫度循環性,而能夠提高壽命。特別是對 於減輕對S i元件之端子部的應力的負擔的意義極大。圖 1 3爲在利用共聚物粒子作爲金屬球來連接後的斷面模型 ,在共聚物粒子60上實施鍍Ni ,更在其上實施鍍Au 的表面處理層6 1 ,而表示以S η焊劑來加熱的連接部。 此時,A u會在焊劑中擴散而形成A u — S η的化合物, 更者,Sn會與Ni反應而Ni - Sn化合物會被形成在 7中,連接部5則會被高熔點化而被連結。 此外,C S P、覆晶(flipchip )等的安裝則大多使用 在移動式製品上。因此,在連接後,藉由塡充具有適當物 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 18 - 1243082 A7 B7 五、發明説明(》6 (請先閲讀背面之注意事項再填寫本頁) 性的樹脂,可以確保1局信賴性°樹脂的熱膨脹係數在1 5 〜4 〇 X 1 0 — 6 / °c的範圍內’最好是在接近於突部的 20χ 1〇一 6/°〇左右’楊氏率爲1〇〇〜2000 k g f /m m 2 ’而爲了要減少對元件的影響,則最好是 4〇〇〜l〇0〇kgf/mm2(實施例4)。利用本發 明的電極構成,而進行溫度階層連接的例子則表示在圖 1 4。而此是以金屬球、焊劑以及其化合物將S i晶片 2 1的電極2 2與被稱爲插入物(interposer )的中間基板 2 3的電極2 4加以連接2 5而得到連接構造體2 6。將 該連接構造體2 6利用熔點爲2 2 0 °C左右的S η - A g —C u 系焊劑 2 7 (例如 S η — 3 A g — 0 . 5 C u (熔 點:2 2 1〜2 1 7 °C )),而連接到玻璃環氧基板2 8 的電極2 9。在連接連接構造體2 6與玻璃環氧基板2 8 時,則是在氮氣回焊爐中在連接部的到達溫度成爲2 3 5 °C的情形下進行焊接,但連接構造體2 6的連接部2 5可 以在較該連接部形成時的溫度爲高的溫度下維持連接狀態 經濟部智慧財產局員工消費合作社印製 ,而不會再熔化、或不會產生剝離,而能夠維持安定的狀 態。 此時,本發明的連接部2 5,當無法承受在s i晶片 2 1與中間基板2 3之間的應力時,則可將樹脂3 0封入 到中間基板2 3之間,而該發生在連接部2 5的應力分散 〇 又,除了 S i晶片2 1之外,利用本發明的方式將多 個的晶片、或晶片零件等一起連接到該中間基板2 3上, T紙張尺度適用中國國家標準(CNS ) A4規格(21QX297公羡).19^ ~ 1243082 A7 B7_ 五、發明説明()17 而能夠提供具有1個功能的模組。 (請先閱讀背面之注意事項再填寫本頁) 圖1 5係表將本發明應用在R F模組的例子。藉由導 電性塗料1 〇 3、線接合(W i r e b ◦ n d i n g ) 1 0 4將被稱爲 S A W濾波器的L T等的半導體晶片1 0 1連接到由陶瓷 所構成的配線基材1 0 2 ’而爲了要保護半導體晶片乃設 置蓋1 0 5。雖然是將該模組1 0 6、晶片零件1 0 7、 線圈零件1 0 8等連接到由玻璃環氧所構成的中間基板 1 0 9,但在連接時,也可以利用金屬球與焊劑的混合塗 料來連接1 1 0。同時整體的蓋1 1 1也可以連接到中間 基板1 0 9 ,由於連接部1 1 〇藉由焊劑與金屬球的反應 而高熔點化,因此,利用中間基板的電極1 1 2可以藉由 其他的焊劑而連接到主機板。 (實施例5 ) 將使用用於連接電極彼此之本發明之連接部的其他的 例子表示在圖1 6。而此爲一在基板中形成由金屬所構成 的熱擴散路徑而讓熱逃走的構造的例子。圖1 6 ( 1 )爲 經濟部智慧財產局員工消費合作社印製 從S i晶片3 1的正上方所看到之電極之配置的說明圖。 在該例子中,信號用的電極3 2則被配置在S i晶片3 1 之外周的3列,而內部的電極是一安裝用來讓熱逃走的熱 擴散用電極3 3。有關該S i晶片3 1對於基板3 4的連 接部,則將圖1 6 ( 1 )的a - a ’斷面表示在圖1 6 ( 2 ),而與和熱擴散用電極3 3對應的基板3 4側的電極 3 5相接地形成散熱孔(thermal via ) 3 6。該散熱孔3 6 -20- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 1243082 A7 B7 五、發明説明()18 (請先閱讀背面之注意事項再填寫本頁) 則與基板3 4之內側的金屬芯層3 7相連。信號用電極 3 2 '熱擴散用電極3 3則均使用本發明來製作’金屬球 使用C u、焊劑使用S η - 3 A g。在此,焊劑的熱傳導 率,當爲S η — 3 7 P b、P b - 5 S η焊劑時分別約爲 5 5w/mk、36w/mk,而Cu的熱傳導率約爲 39〇w/mk,因此,對於Cu量較多的連接部’其熱 傳導則較使用焊劑之習知的連接部爲優良。更者’熱可以 從散熱良好的連接部3 8的電極,經由散熱孔(thermal vias ) 3 6而擴散到金屬芯層3 7 °因此在根據本發明來連 接時,則經由連接部3 8的熱傳導、散擴散會變得活潑, 對於安裝高輸出元件可說是一極爲優良的方式。 在此,在信號用電極3 2中,接地電極3 9也可以與 基板3 4的金屬芯層3 7同樣地形成孔1 0 0。亦即’金 屬層3 7可以兼作爲基板的地面(ground )。又’散熱孔 36、金屬芯層37、孔100此次雖然是利用Cu來形 成,但也可以利用A 1等來形成。又,相反地,爲了要得 到S i晶片3 1 ( L S I )之充分的性能,則可以選擇金 經濟部智慧財產局員工消費合作社印製 屬球6、散熱孔3 6、金屬芯3 7的材質。 如上所述,本發明由於根據金屬球6的材質可以使其 熱傳導相較於通常的焊劑連接大幅地提升,因此在連接高 輸出的S i晶片、連接狹窄間距的L S I時,則可以適合 維持S i晶片(L S I )的性能。具體的例子則是適合於 被搭載在汽車車內之電子機器等的連接構造。又,即使是 如圖1 5所示的R F模組,由於頻率會因爲熱而產生偏移 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -21 - 1243082 A7 B7 五、發明説明()19 (請先閲讀背面之注意事項再填寫本頁) ’因此該製品具備散熱特性優良的連接部則對於維持模組 的性能非常的重要。又,如本實施例所示,本發明的電極 構造不只是信號用電極,也可以當作散熱用電極來使用。 更者,當同時使用具有金屬芯層的基板等時,則更具散熱 效果。 根據上述的各實施例,可以供給以往在製造電子機器 時所使用之熔點高,且含有許多鉛之高鉛焊劑的替代材料 。該材料的連接溫度可爲低溫,而可以藉由熔點爲2 2 〇 °C左右的S η - A g - C u系的無鉛焊劑等來實施溫度階 層連接。又,可以得到一能夠耐得住因爲零件、基板材料 的膨脹係數差而在電極部所產生的應力的電極構造。又, 藉由使用此,可以減輕對於環境所造成的負荷。更者,由 於是一熱傳導性高的金屬多的構造,因此,經由突出部的 熱傳導、熱散熱會變得活潑,可說是一對於安裝高輸出元 件爲優越的方式。 經濟部智慧財產局員工消費合作杜印製 根據本發明可以提供一在電子零件內當作電極來使用 而含鉛多且熔點高之焊劑的替代材料、以及使用此之連接 方法、電子機器。特別是可以提供一可用於被稱爲C 4連 接之形狀之電極等的無鉛材料、以及使用此的連接方法。 上述記載雖然是根據實施例而實施,但從事該行業者 可以在其精神與申請專利範圍的範圍內作各種的變更以及 修正。 圖面之簡單說明: 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 22 - 1243082 A7 _B7___ 五、發明説明(如 圖1爲本發明之安裝構造體的說明圖。 圖2爲本發明之電極間之連接部之構成的說明圖。 (請先閲讀背面之注意事項再填寫本頁) 圖3爲連接部的形狀爲直方體、圓柱狀、或腰(waist )形狀的例子。 圖4爲圖1所示之電子機器之製程的說明圖。 圖5爲圖1所示之電子機器之製程的說明圖。 圖6爲在圖4所示之製程之第2過程加熱之前之混合 塗料供給時之狀態的說明圖。 圖7爲助熔劑成分在連接後當作塡平劑(underfill )來 使用的例子。 圖8爲連接部5藉由金屬顯微鏡的觀察結果的說明圖 〇 圖9爲模式地來表示連接部5的說明圖。 圖1 0爲本發明之電極間之連接部之其他例子的說明 圖。 圖11爲在使用本發明之半導體晶片上之電極之製程 的說明圖。 經濟部智慧財產局員工消費合作社印製 圖1 2爲本發明之其他之製程的說明圖。 圖1 3爲利用共聚物粒子(p〇lymer beads )之連接部的 說明圖。 圖1 4爲將本發明應用在溫度階層連接之例子的說明 圖。 圖1 5爲將本發明應用在R F模組之例子的說明圖。 圖1 6爲針對本發明的構造更加提升散熱特性之例子 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -23 _ 1243082 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明( 的說明圖。 元件對照表 1 :半導體晶片 3,4 :電極 6 :金屬球相 8 :金屬間化合物相 1 0 :焊劑球 1 2 :密封樹脂 1 4 :焊劑球 1 6 :配線突部 1 8 :連接部 2〇:樹脂 4 1 : 晶片 4 3 :表面保護膜 4 5 :金屬多層膜 4 7 :電極墊 4 9 : S i晶片 2 3 :中間基板 2 6 :連接構造體 2 8 :玻璃環氧基板 3 2 :信號用電極 3 4 :基板側 3 6 :散熱孔 2 :中間基板 5 :連接部 7 :焊劑相 9:混合塗料 11:助熔劑成分 1 3 :電極 15:印刷配線基板 1 7 :迎面焊劑 19:安裝構造體 4 0 :晶圓 4 2 :電極墊 4 4 :光阻膜 4 6表面保護膜 4 8 :突部2 1 : S i晶片 2 5 ;連接部 2 7 :焊劑3 1 : S i晶片 3 3 :熱擴散用電極 3 5 :電極 3 7 :金屬芯層 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -24- 1243082 A7 B7 五、發明説明(谇 3 8 :連接部 1 0 1 :半導體晶片 1 0 3 :導電性塗料 1〇5 :蓋 1 〇 7 :晶片零件 1 0 9 :中間基板 1 1 1 :蓋 3 9 :接地電極 1 0 2 :配線基材 1 0 4 .線接合 1 0 6 :模組 1 0 8 :線圏零件 1 1〇:連接 1 1 2 :中間基板的電極 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 25- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
Claims (1)
- 8 8 8 8 ABCD 12430! 六、申請專利範圍 第9 1 1 0 7 8 7 8號專利申請案 中文申請專利範圍修正本 (請先閱讀背面之注意事項再填寫本頁) 民國93年9月13日修正 1 · 一種電子機器,其特徵在於: 電子零件的電極與基板之電極間的連接部則是以由 S η或I η之其中一者所構成的相來連結單體金屬、合金 、化合物或包含該些混合物在內的金屬球相。 2 · —種電子機器,其特徵在於: 電子零件的電極與基板之電極間的連接部則是以s η 或I η之其中一者的焊劑相與由和該金屬球相的反應所產 生之金屬間化合物相及/或以該焊劑相與該金屬間化合物 相兩者來連結單體金屬、合金、化合物或含有該些混合物 的金屬球相。 3 · —種電子機器,其特徵在於: 電子零件的電極與基板的電極間的連接部,則是以從 Sn — Cu系焊劑,Sn-Ag系焊劑、Sn - Ag — 經濟部智慧財產局員工消費合作社印製 C u系焊劑,在該些添加了 I ]Ί、z η、B i之其中一個 以上的焊劑所構成的群中所選擇的一種以上的相來連結單 體金屬、合金、化合物、或含有該些混合物的金屬球相。 4 · 一種電子機器,其特徵在於: 電子零件的電極與基板的電極間的連接部,則是以從 S η — C u系焊劑,S η — A g系焊劑、s η — A g — C u系焊劑,在該些添加了 I η、ζ η、B i之其中一者 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 8 8 8 8 ABCD 經濟部智慧財產局員工消費合作社印製 1243082 π、申請專利範圍 以上的焊劑所構成的群中所選擇的一種以上的焊劑相、與 由和該金屬球相的反應所產生的金屬間化合物相及/或以 該焊劑相與金屬間化合物兩者來連結單體金屬、合金、化 曰物或含有該些混合物的金屬球相。 5 .如申請專利範圍第1項至第4項中任一項之電子 機器,其中上述金屬球相包含從由C u、A g、A u、 A 1 、Ni 、Cu 合金、Cu — Sn 化合物、Ag - Sn 化合物、A u — S n化合物、A 1 - A g化合物、z n - A 1化合物、或該些的混合物所構成的群中所選出的一種 以上。 6 ·如申請專利範圍第1項至第4項中任一項之電子 機器,其中上述金屬球相則是在金屬球相之芯部的周圍具 有從由Au層、Ag層、S η層的單體金屬層、含有S n 的口金層、被接合到芯部的N i層與被接合到N i層的 A u層、以及被接合到芯部的n i層與被接合到N 1層的 A g層所構成的群中所選擇之其中一者的被覆。 7 · —種電子機器,其特徵在於: 在連接電子零件的電極與基板的電極間時,則將由單 體金屬、合金、化合物或含有該些混合物的金屬球,含有 S η 、或I η之其中一者的焊劑球混合而成的塗料供給到 該電極間,將該些加熱,藉著將該焊劑球成分熔化來連結 該金屬球之間、以及該金屬球與該電子零件的電極,該基 板的電極間。 8 · —種電子機器,其特徵在於: 本紙張尺度適用中國國家摞準(CNS ) Α4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁)A8 B8 C8 D8 1243082 六、申請專利範園 (請先閱讀北e面之注意事項再填寫本頁} 在連接電子零件的電極與基板的電極間時,將由含有 從由單體金屬、合金、化合物、以及該些混合物所構成之 群中所選擇之一種以上的金屬球、與從由S η — c U系焊 劑,S η - A g系焊劑、S η — A g — C u系焊劑,在該 些添加了 I η、Ζ η、B 1之其中一個以上的焊劑所構成 的群中所選擇的一種以上混合而成的塗料供給到該電極間 ,將該些加熱’藉著讓該焊劑球成分熔化來連結該金屬球 之間、以及該金屬球與該電子零件的電極,該基板的電極 間。 9 ·如申請專利範圍第7項或第8項之電子機器,g 中上述金屬球含有由(:1:1、人忌、八11、八1、1^1、 Cu合金、Cu - Sn合金、Ag — Sn合金、Au〜 S η化合物、A 1 - A g化合物、Ζ η - A 1化合物、以 及該些混合物所構成的群中所選出的一種以上。 f 經濟部智慧財產局員工消費合作社印製 1 〇 ·如申請專利範圍第7項或第8項之電子機器, 其中在上述金屬球實施從由鍍A u、鍍A g、鍍S n的單 體金屬、鍍含有Sη的合金、2層電鍍爲底層鍍Ni ,而 在其表面實施鍍A u 、以及底層鍍N i ,而在其表面實施 鍍A g所構成的群中所選擇的一個被覆。 1 1 ·如申請專利範圍第1項至第4項中任一項之電 子機器,其中上述連接部的形狀爲從由桶狀、圓柱狀、直 方體、以及腰狀所構成的群中所選擇的一個° 1 2 · —種電子機器,其特徵在於: 第1項至第1 1項之任一項之電子機器的基板具有合 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 3- 1243082 A8 B8 C8 D8 々、申請專利範圍 屬芯層。 焊 鉛 無 用 利 口吝 : 機 <、、子 Ξ電 在之 徵1^ 特 7 其任 哩S之 网目 造項 構 2 ο 裝1板 安第基 種至的 一 項他 • 1 其 3 第在 1將裝 安 劑 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
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-
2001
- 2001-04-18 JP JP2001119030A patent/JP4051893B2/ja not_active Expired - Fee Related
-
2002
- 2002-04-12 US US10/469,215 patent/US20040177997A1/en not_active Abandoned
- 2002-04-12 WO PCT/JP2002/003676 patent/WO2002087297A1/ja active Application Filing
- 2002-04-17 TW TW091107878A patent/TWI243082B/zh not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI414049B (zh) * | 2009-07-16 | 2013-11-01 | Renesas Electronics Corp | 半導體裝置之製造方法 |
US8633103B2 (en) | 2009-07-16 | 2014-01-21 | Renesas Electronics Corporation | Semiconductor device and manufacturing method of the same |
Also Published As
Publication number | Publication date |
---|---|
JP2002314241A (ja) | 2002-10-25 |
JP4051893B2 (ja) | 2008-02-27 |
WO2002087297A1 (fr) | 2002-10-31 |
US20040177997A1 (en) | 2004-09-16 |
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