CN112820708A - 半导体装置用铜合金接合线 - Google Patents
半导体装置用铜合金接合线 Download PDFInfo
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- CN112820708A CN112820708A CN202110066731.6A CN202110066731A CN112820708A CN 112820708 A CN112820708 A CN 112820708A CN 202110066731 A CN202110066731 A CN 202110066731A CN 112820708 A CN112820708 A CN 112820708A
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- wire
- bonding
- mass
- copper alloy
- bonding wire
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 59
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 40
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 33
- 239000005751 Copper oxide Substances 0.000 claims description 32
- 229910000431 copper oxide Inorganic materials 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 239000011162 core material Substances 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 238000011156 evaluation Methods 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000007547 defect Effects 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000005491 wire drawing Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- 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
- H01L24/01—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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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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
- H01L23/49—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 wire-like arrangements or pins or rods
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- 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
- H01L24/01—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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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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
- B23K35/02—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
- B23K35/0227—Rods, wires
-
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H01L24/01—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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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- H01L24/74—Apparatus for manufacturing arrangements for connecting or disconnecting semiconductor or solid-state bodies
- H01L24/741—Apparatus for manufacturing means for bonding, e.g. connectors
- H01L24/745—Apparatus for manufacturing wire connectors
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- 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
- H01L24/85—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 wire connector
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- H—ELECTRICITY
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- 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
- H01L2224/056—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
- H01L2224/05617—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 400°C and less than 950°C
- H01L2224/05624—Aluminium [Al] as principal constituent
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- H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
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- H01L2224/45001—Core members of the connector
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- H01L2224/451—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
- H01L2224/45101—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
- H01L2224/45105—Gallium (Ga) as principal constituent
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- 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
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- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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- H01L2224/451—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
- H01L2224/45101—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
- H01L2224/45109—Indium (In) as principal constituent
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- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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- H01L2224/451—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
- H01L2224/45117—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 400°C and less than 950°C
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Abstract
在半导体装置用的铜合金接合线中,实现高温高湿环境下的球部接合寿命的提高。一种半导体装置用铜合金接合线,其特征在于,总计含有0.03质量%以上3质量%以下的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素(第1元素),其余部分由Cu和不可避免杂质构成。通过含有预定量的第1元素,从而在线接合界面中抑制在高温高湿环境下容易腐蚀的金属间化合物的生成,提高球部接合寿命。
Description
本申请是申请日为2018年12月17日、申请号为201780037612.X、发明名称为“半导体装置用铜合金接合线”的发明专利申请的分案申请。
技术领域
本发明涉及用于对半导体元件上的电极和外部导线等电路布线基板的布线进行连接的半导体装置用铜合金接合线。
背景技术
当前,作为对半导体元件上的电极与外部导线之间进行接合的半导体装置用接合线(以下,称为“接合线”),主要使用线径15~50μm左右的细线。接合线向半导体装置的电极的接合方法一般是超声波并用热压接方式,使用通用接合装置、以及使接合线通过其内部以用于连接的劈刀(capillary)夹具等。接合线的接合工艺如下:利用电弧热量输入来加热熔融线尖端,并利用表面张力形成球(FAB:Free Air Ball:自由空气球)后,在加热到150~300℃的范围内的半导体元件的电极上压着接合该球部(以下,称为“球接合”),接着,在形成了线弧后,将线部压着接合(以下,称为“楔接合”)到外部导线侧的电极上,从而完成。对于作为接合线的接合对象的半导体元件上的电极,使用在Si基板上成膜有以Al为主体的合金的电极结构,对于外部导线侧的电极,使用施加有镀Ag或镀Pd的电极结构等。
迄今为止,接合线的材料以金(Au)为主流,但是,以LSI用途为中心而向铜(Cu)的替代正在进展。另一方面,以近年来的电动汽车或混合动力汽车的普及为背景,在车载用设备用途中,对从Au向Cu的替代的需求也正在提高。
关于铜接合线,提出了使用高纯度Cu(纯度:99.99质量%以上)的铜接合线(例如专利文献1)。在使用铜接合线的情况下,也在高密度安装中要求接合可靠性、线弧的稳定性较高。接合可靠性评价是出于对实际的半导体器件的使用环境中的接合部寿命进行评价的目的而进行的。一般而言,对于接合可靠性评价,使用高温放置试验、高温高湿试验。高温高湿试验一般使用在温度为121℃、相对湿度为100%的条件下进行的被称为PCT(PressureCooker Test:压力锅试验)的试验。
在专利文献2中,记载了由含有0.13~1.15质量%的浓度范围的Pd的铜合金构成的半导体用铜合金接合线。通过在上述浓度范围中添加Pd,从而能够提高PCT试验所得到的高湿加热可靠性。
现有技术文献
专利文献
专利文献1:日本特开昭61-48543号公报
专利文献2:国际公开第2010/150814号
发明内容
发明要解决的课题
车载用设备与一般的电子设备相比,要求严苛的高温高湿环境下的接合可靠性。尤其是,将线的球部接合在电极上的球接合部的接合寿命成为最大的问题。提出了几种对高温高湿环境下的接合可靠性进行评价的方法,作为近年代表性的评价方法,使用HAST(Highly Accelerated Temperature and Humidity Stress Test)(高温高湿环境暴露试验)。HAST具有向评价封装的吸湿均匀、且评价结果的再现性较高这样的特征。在利用HAST来评价球接合部的接合可靠性的情况下,通过将评价用的球接合部暴露在温度为130℃、相对湿度为85%的高温高湿环境中,测定接合部的电阻值的经时变化、或者测定球接合部的剪切强度的经时变化,从而评价球接合部的接合寿命。此外,通过施加偏置电压,从而能够进行比PCT更严格的评价。最近,变成了在这样的条件下的HAST中要求100小时以上的接合寿命。
本发明的目的在于提供一种在接合线中改善高温高湿环境下球接合部的接合可靠性、并适合于车载用设备的半导体装置用接合线。具体而言,本发明发现了即使在更严格的评价方法即施加了偏置电压的HAST中也具有充分的接合可靠性的对于铜合金接合线的最佳的添加元素及其最佳的添加浓度。
用于解决课题的手段
即,本发明的主旨之处如下。
(1)一种半导体装置用铜合金接合线,其特征在于,总计含有0.03质量%以上3质量%以下的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素,其余部分由Cu和不可避免杂质构成。
(2)如(1)所述的半导体装置用铜合金接合线,其特征在于,当将线的线径设为R(μm)时,上述铜合金接合线的垂直于线轴的方向的芯材截面中的平均结晶粒径(μm)为:
0.02×R+0.4以上(1a)
0.1×R+0.5以下(1b)。
(3)如(1)或(2)所述的半导体装置用铜合金接合线,其特征在于,线表面的氧化铜的平均膜厚为0.0005~0.02μm的范围。
(4)如(1)~(3)的任一项所述的半导体装置用铜合金接合线,其特征在于,上述铜合金接合线进一步含有相对于线整体分别为0.0001~0.050质量%的选自Ti、B、P、Mg、Ca、La、As、Te、Se的至少1种以上的元素。
(5)如(1)~(4)的任一项所述的半导体装置用铜合金接合线,其特征在于,上述铜合金接合线进一步含有相对于线整体总计为0.0005~0.5质量%的选自Ag、Au的至少1种以上的元素。
(6)如(1)~(5)的任一项所述的半导体装置用铜合金接合线,其特征在于,上述铜合金接合线进一步含有1.15质量%以下的Pd。
(7)如(1)~(6)的任一项所述的半导体装置用铜合金接合线,其特征在于,上述铜合金接合线含有2种以上的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的元素。
发明效果
根据本发明,通过在半导体装置用的铜合金接合线中含有总计为0.03质量%以上3质量%以下的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素,从而能够提高高温高湿环境下的球接合部的接合寿命,并改善接合可靠性。
具体实施方式
《第1元素及其效果》
本发明的半导体装置用铜合金接合线(以下,也简称为“接合线”。)的特征在于,通过对铜合金进行拉丝而形成,该铜合金总计含有0.03质量%以上3质量%以下的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素(也称为“第1元素”。),其余部分由Cu和不可避免杂质构成。本发明的接合线因为是以铜为主体的合金,所以也称为“铜合金接合线”。本发明的半导体装置用铜合金接合线是不具有以铜以外的金属为主成分的被覆层的接合线,也称为“裸Cu合金线”。本发明的接合线能够改善车载用设备所要求的高温高湿环境下的球接合部的接合可靠性。
半导体装置的封装即模制树脂(环氧树脂)在分子骨架中含有氯(Cl)。在作为HAST评价条件的130℃、相对湿度为85%的高温高湿环境下,分子骨架中的Cl会水解而作为氯离子(Cl-)溶出。在将铜合金接合线接合在Al电极上的情况下,当Cu/Al接合界面被置于高温下时,Cu和Al会相互扩散,最终形成作为金属间化合物的Cu9Al4。Cu9Al4容易受到Cl等卤素的腐蚀,腐蚀会因从模制树脂溶出的Cl而进展,关系到接合可靠性的降低。因此,在以往的铜合金接合线中,HAST评价中的球接合部寿命不足。
对此,如本发明这样铜合金接合线通过总计含有0.03质量%以上的第1元素(选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素),从而对于使用了该铜合金接合线的球接合部,HAST评价中的球接合部寿命提高。认为当总计含有0.03质量%以上的第1元素时,具有接合部的Cu9Al4金属间化合物的生成被抑制的倾向。认为存在于球接合部的Cu与Al界面的第1元素提高Cu和Al的相互扩散抑制效果,结果,抑制在高温高湿环境下容易腐蚀的Cu9Al4的生成。此外,线中含有的第1元素也可能具有直接阻碍Cu9Al4的形成的效果。认为接合界面附近的第1元素的作用是对诱发腐蚀的卤素的移动进行阻碍的屏障功能、对Cu、Al的相互扩散及金属间化合物的成长等进行控制的功能等。
进而,在使用含有预定量的第1元素的铜合金接合线来形成球部、并用扫描电子显微镜(SEM:Scanning Electron Microscope)观察FAB时,在FAB的表面看到多个直径几十nm左右的析出物。当用能量色散型X线分析(EDS:Energy Dispersive X-ray Spectroscopy)进行分析时,确认了第1元素稠化。从以上那样的状况,不清楚详细的机理,但是,认为由于在FAB下观察的该析出物存在于球部与电极的接合界面上,从而温度为130℃、相对湿度为85%的高温高湿环境下的球接合部的接合可靠性显著提高。从在比PCT评价更严格的条件即HAST评价中得到良好的结果而显而易见,本发明的接合线在PCT评价中也能够得到良好的结果。
从提高温度为130℃、相对湿度为85%的高温高湿环境下的球接合部的接合寿命、并改善接合可靠性的观点考虑,线中的第1元素的含量(也称为“浓度”)总计为0.03质量%以上,优选为0.050质量%以上,更优选为0.070质量%以上,进一步优选为0.090质量%以上、0.100质量%以上、0.150质量%以上、或0.200质量%以上。当线中的第1元素的浓度总计为0.100质量%以上时,能够对应对于更严格的接合可靠性的要求。
另一方面,从得到良好的FAB形状的观点考虑,从抑制接合线的硬质化以得到良好的楔接合性的观点考虑,线中的第1元素的浓度总计为3质量%以下,优选为2.5质量%以下,更优选为2.0质量%以下,进一步优选为1.9质量%以下、或1.5质量%以下。此外,通过这样规定第1元素的含量的上限,从而低温接合中的与Al电极的初始接合强度良好,从得到HAST试验中的长期可靠性、或向BGA(Ball Grid Array:球栅阵列)、CSP(Chip SizePackage:芯片级封装)等基板、带等的接合的量产余量(margin)优异的接合线的观点考虑,以及从减少芯片损伤的观点考虑,能够得到良好的结果。当第1元素的含量超过3.0质量%时,为了不使芯片损伤产生,需要以低载荷进行球接合,与电极的初始接合强度会降低,结果,有的情况下HAST试验可靠性会恶化。在本发明的接合线中,通过将第1元素的含量(浓度)的总计设为上述优选的范围,从而HAST试验中的可靠性进一步提高。例如,能够实现到HAST试验发生不良为止的寿命超过250小时的接合线。这在有的情况下相当于以往的Cu接合线的1.5倍以上的长寿命化,也能够对应在严苛的环境下的使用。
从实现在温度为130℃、相对湿度为85%的高温高湿环境下的球接合部的接合寿命方面显著优异的铜合金接合线观点考虑,本发明的半导体装置用Cu合金接合线优选含有2种以上的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的元素(第1元素)。其中,作为第1元素的组合,优选Ni和Zn、Ni和Ga、Ni和Ge、Ni和In、Pt和Zn、Pt和Ga、Pt和Ge、Pt和In、Ir和Zn、Ir和Ge、Rh和Ga、Rh和In、Ni和Pt和Zn、Ni和Pt和Ga、Ni和Pt和Ge、Ni和Pt和In、Pt和Ir和Zn、Pt和Ir和Ga、Ir和Rh和Ge、Ir和Rh和In等组合。
《接合线的平均粒径》
评价了接合线中的结晶粒径对线质量产生的影响。结果,判明了垂直于接合线的线轴的方向的芯材截面中的平均结晶粒径存在优选范围,在设线的线径为R(μm)时,在平均结晶粒径(μm)为
0.02×R+0.4以上 (1a)
0.1×R+0.5以下 (1b)
时,球接合部的塌陷形状、或楔接合性特别良好。
在测定结晶粒径时,优选使用电子背散射衍射法(EBSD、Electron Backscattered Diffraction)。对于粒径测定,能够通过对基于EBSD法的测定结果利用装置所装备的分析软件来出求。本发明中规定的结晶粒径是对测定区域内所含有的结晶粒的当量直径(与结晶粒的面积相当的圆的直径)进行算术平均的结果。
《线表面的氧化铜的平均膜厚》
在本发明中优选将线表面的氧化铜的平均膜厚设为0.0005~0.02μm的范围。在总计以0.03~3质量%的浓度范围含有第1元素的铜合金接合线中,如果线表面的氧化铜的平均膜厚为0.0005~0.02μm的范围,则能够进一步提高使HAST可靠性以量产水平稳定地提高的效果。当线表面的氧化铜的膜厚比0.02μm厚时,由含有第1元素的铜合金构成的接合线的球接合部的HAST可靠性的改善效果会产生偏差,HAST加热后的接合强度等存在变得不稳定的倾向。该HAST可靠性的偏差在线径为20μm以下的接合线中有可能更成为问题。关于含有第1元素的铜合金的表面的氧化铜使HAST可靠性不稳定化的主要原因,尽管仍有不明点,但是可以认为铜合金接合线的长度方向或从线表面起的深度方向上的第1元素的浓度分布变得不均匀、或者球内部的侵入氧或残留氧化物有可能阻碍第1元素的HAST可靠性的提高效果等。根据含有第1元素的铜合金接合线,因为能够得到使表面氧化延迟的效果,所以容易将氧化铜的平均膜厚控制在较薄的范围即0.0005~0.02μm。还确认了,在总计以0.03~3质量%的浓度范围含有第1元素的铜合金接合线中,与高纯度铜相比较,具有使20~40℃左右的低温区域中的线表面的氧化铜膜的成长延迟的作用。
因为当线表面的氧化铜的平均膜厚超过0.02μm时,如上所述,HAST评价的改善效果容易产生偏差,例如,当增加评价的接合数时,改善效果会产生偏差而变得不稳定的可能性提高,优选所以线表面的氧化铜的平均膜厚的上限设为0.02μm。从能够减少改善效果的偏差这样的观点考虑,线表面的氧化铜的平均膜厚优选为0.02μm以下,更优选为0.015μm以下,进一步优选为0.013μm以下。另一方面,因为为了将线表面的氧化铜的平均膜厚稳定地抑制为小于0.0005μm,需要特殊的表面处理、产品管理等,会诱发接合性的降低、成本上升等,工业上的应用变得困难,所以优选线表面的氧化铜的平均膜厚的下限设为0.0005μm。例如,当出于将氧化铜的平均膜厚抑制为小于0.0005μm的目的,而将线表面的防锈剂的涂布膜加厚时,会存在接合强度降低而连续接合性降低这样的问题。此外,因为如果出于将氧化铜的平均膜厚抑制为小于0.0005μm的目的,而将线产品的大气保管的保证寿命极端地缩短,则引线接合的量产工序中的操作变得困难,会产生废料问题,所以有的情况下在工业上不会被容忍。从能够提供工业上合适的接合线这样的观点考虑,线表面的氧化铜的平均膜厚优选为0.0005μm以上,更优选为0.0008μm以上,进一步优选为0.001μm以上。
关于线表面的氧化铜的平均膜厚的测定,适用于表面分析的俄歇光谱分析是有效的,希望使用在线表面的随机的位置的最低3处以上、如果可能则是5处以上测定的氧化铜的膜厚的平均值。所谓氧浓度,使用O浓度相对于总计了Cu、O、金属元素的浓度的比率。因为将作为线表面的代表性的污染的有机物除外,所以在上述的浓度计算中,不包含C量。因为高精度地求出氧化铜的膜厚的绝对值是困难的,所以希望使用在俄歇光谱法中一般使用的SiO2换算值来算出氧化铜膜厚。在本发明中,将氧浓度为30质量%作为氧化铜与金属铜的交界。已知主要的氧化铜为Cu2O、CuO,但是,因为在含有第1元素的铜合金的表面,在低温(25~500℃)时优先形成Cu2O的情况较多,所以将氧浓度为30质量%作为交界。
《第2元素及其效果》
本发明的接合线优选进一步相对于线整体分别含有0.0001~0.050质量%的选自Ti、B、P、Mg、Ca、La、As、Te、Se的至少1种以上的元素(也称为“第2元素”)。由此,能够改善高密度安装所要求的球接合部的塌陷形状,即改善球接合部形状的正圆性。另外,由此,能够实现更良好的球形状。从能够提高使球接合部的压着形状正圆化的效果的观点考虑,优选第2元素的含量(浓度)总计为0.0001质量%以上,更优选为0.0002质量%以上,进一步优选为0.0003质量%以上。此外,从抑制球的硬质化以抑制球接合时的芯片损伤的观点考虑,优选第2元素的含量为0.050质量%以下,更优选为0.045质量%以下,进一步优选为0.040质量%以下。此外,因为通过分别含有0.0005质量%以上的该第2元素,从而得到使楔接合部的不良发生减少的效果,所以更优选。通过添加第2元素,从而在线变形时减轻线的加工硬化,能够提高促进楔接合的线变形的作用。虽然不清楚详细的机理,但是,可认为第1元素固溶在Cu中,第2元素因为在Cu中的固溶度较小而析出、偏析,从而这些元素补充性地进行作用,能够对楔接合的线变形发挥更加优异的效果。
《第3元素及其效果》
本发明的接合线优选进一步含有总计0.0005~0.5质量%的选自Ag、Au的至少1种以上的元素(也称为“第3元素”。)。在最近的高密度安装所要求窄间距连接中,球接合部的变形形状是重要的,要求抑制花瓣状、偏芯等异形以使其正圆化。通过将第3元素和第1元素并用地添加,从而能够容易使球变形各向同性,提高使压着形状正圆化的效果。由此,确认了对于50μm以下的窄间距连接也能够充分适应。如果第3元素含量总计为0.0005质量以上,则更有效地发挥该效果。从能够提高使球接合部的压着形状正圆化的效果的观点考虑,优选第3元素的含量总计为0.0005质量%以上,更优选为0.0007质量%以上,进一步优选为0.001质量%以上。此外,从得到良好的FAB形状这样的观点考虑,优选第3元素的含量为0.5质量%以下,更优选为0.4质量%以下,进一步优选为0.3质量%以下。另一方面,当第3元素的含量总计超过0.5质量%时,存在FAB形状会恶化的风险。当使接合线含有Au时,重结晶温度会上升,因为防止拉丝加工中的动态重结晶,所以加工组织变得均匀,热处理后的结晶粒尺寸变得比较均匀。由此,线的断裂伸长率提高,在接合时能够形成稳定的线弧。在进一步含有Au的情况下,优选决定含量,以使得线中的第1元素的总计超过0.1质量%。本发明的接合线既可以同时含有第2元素和第3元素,也可以代替第2元素而含有第3元素。
《Pd的含有及其效果》
本发明的接合线优选进一步以1.15质量%以下的范围含有Pd。由此,能够进一步提高球接合部的高湿加热可靠性。可以认为,通过在接合线中以上述浓度范围含有Pd,从而Pd扩散或稠化到接合界面,通过对Cu与Al的相互扩散产生影响,从而使在球接合部接合界面上成长的Cu-Al系的金属间化合物的腐蚀反应延迟。从能够显著提高HAST可靠性的观点考虑,优选Pd的含量为1.15质量%以下,更优选为1.0质量%以下,进一步优选为0.9质量%以下。另一方面,当Pd浓度超过1.15质量%时,由于线的常温强度、高温强度等会上升,从而有时会出现线弧形状的偏差的发生、楔接合性的降低等,因此优选Pd含量上限设为1.15质量%。本发明的接合线既可以同时含有第2元素及/或第3元素和Pd,也可以代替第2元素及第3元素的任一者或两者而含有Pd。
《接合线的制造方法》
说明本发明的半导体装置用接合线的制造方法的概要。
使用铜纯度为4N~6N(99.99~99.9999质量%)的高纯度铜,并通过熔解来制作含有必要的浓度的添加元素的铜合金。在进行熔解时,能够利用电弧加热炉、高频加热炉、电阻加热炉等。为了防止来自大气中的O2、H2等气体的混入,优选在真空环境或者Ar或N2等非活性环境中进行熔解。然后,在炉中进行缓冷而制作坯料(铸块)。为了清洗坯料表面,而进行酸洗及水洗,并使其干燥。对于铜中的添加元素的浓度分析,ICP(Inductively CoupledPlasma:感应耦合等离子体)分析等是有效的。
在该合金化中,存在直接添加高纯度的成分的方法、利用含有1%左右的高浓度的添加元素的母合金的方法。利用母合金的方法因低浓度地含有而对于使元素分布均匀化是有效的。在本发明的添加成分中,在以0.5质量%以上的比较的高浓度含有第1元素的情况下,能够利用高纯度的直接添加,而为了低浓度地稳定地含有第1元素及第2元素,添加母合金的方法是有利的。
在使接合线中含有第1元素、第2元素、第3元素、其它元素时,如上所述,除了在熔解时使其含有这些元素的方法之外,即使采用使合金元素覆着在接合线表面上而含有的方法,也能够发挥上述本发明的效果。
也能够在线制造工序的中途,使合金成分覆着在线表面上从而使其含有合金成分。在此情况下,既可以插入到线制造工序的某处,也可以重复多次。也可以插入在多个工序中。作为覆着方法,能够从(1)水溶液的涂布、干燥、热处理、(2)镀敷法(湿式)、(3)蒸镀法(干式)中选择。
制造出来的铜合金块首先通过轧制而被加工成大径,接着通过拉丝加工而被变细到最终线径。在轧制工序中,使用槽型辊或模锻等。在拉丝工序中,使用能够设置多个钻石包覆的模具的连续拉丝装置。根据需要,在加工的中途阶段或以最终线径实施热处理。
当使铜合金接合线含有第1元素时,线的材料强度(硬度)变高。因此,在拉丝加工接合线时,将拉丝时的减面率设为5~8%的较低的减面率。此外,在拉丝后的热处理中,因为仍然硬度较高,所以为了软质化到能够作为接合线来使用的级别,而以700℃以上的温度进行了热处理。因为是较高的热处理温度,所以芯材截面中的平均结晶粒径(μm)为大于(0.1×R+0.5)(R为线径(μm)),楔接合性会稍微降低。另一方面,当降低热处理温度时,结果,芯材截面中的平均结晶粒径(μm)为小于(0.02×R+0.4),球接合部的塌陷形状会稍微降低。
因此,在本发明中,优选在进行使用了模具的拉丝时,对于全模具数中的一半以上的模具将减面率设为10%以上,进而将拉丝后的热处理中的热处理温度设为600℃以下的较低的温度。结果,能够将垂直于接合线的线轴的方向的芯材截面中的平均结晶粒径(μm)设为合适范围(0.02×R+0.4以上、0.1×R+0.5以下)(R为线径(μm))。应用最新的拉丝加工技术,作为润滑液,将在润滑液中含有的非离子系表面活性剂的浓度设计成比以往更高,作为模具形状,模具的接近(approach)角度设计成比以往的接近角度更平缓,将模具的冷却水温度设定成比以往更低等,通过这些的协同作用,从而尽管在铜合金接合线中总计含有0.03质量%以上的第1元素成分而进行了硬质化,仍然能够进行减面率10%以上的拉丝加工。
作为用于将线表面的氧化铜的平均膜厚以量产水平管理在0.0005~0.02μm的范围的制造条件,优选抑制线制造工序中的氧化。对于控制热处理工序中的氧化铜的形成,温度(200~850℃)、热处理工序中的非活性气体流量的调整(1~8L/分)、炉内的氧浓度的管理等是有效的。对于氧浓度,在炉的中央部测定,并进行调整以使得其浓度范围为0.1~6体积%是有效的。作为将氧浓度控制在上述范围的方法,能够通过上述气体流量的优化、改变炉的入口、出口等的形状,从而管理从外界向热处理炉内的大气卷入的防止等。进而,在量产水平下,希望也管理拉丝工序,例如,通过在经过1次水中的拉丝工序后,卷取线之前,进行干燥(40~60℃的温风大气的吹送),从而主动地除去线表面的水分、管理在制造工序中途的保管的湿度(在保管2日以上时相对湿度60%以下)等也是有效的。
实施例
以下,一边示出实施例一边具体说明本发明的实施方式的接合线。
(样品)
首先,说明样品的制作方法。作为芯材的原材料的Cu使用了纯度为99.99质量%以上(在本实施例中使用6N(浓度为99.9999质量%以上的原材料))且其余部分由不可避免杂质构成的原材料。第1元素、第2元素、第3元素及Pd使用了纯度为99质量%以上且其余部分由不可避免杂质构成的原材料。调配作为向芯材的添加元素的第1元素、第2元素、第3元素、Pd的合金元素,以使得线或芯材的组分成为目标组分。关于各元素的添加,能够以单体进行调配,但是,在单体使为高熔点的元素或添加量为极微量的情况下,也可以预先制作含有添加元素的Cu母合金并进行调配以使其成为目标添加量。
对于铜合金,通过连续铸造而以成为几mm的线径的方式进行了制造。对于得到的几mm的合金,进行拉拔加工而制作了φ0.3~1.4mm的线。对于拉丝,使用市售的润滑液,拉丝速度设为20~150m/分。除了一部分的实施例之外,通过在为了去除线表面的氧化膜而利用盐酸等进行了酸洗处理后,对于全模具数量中的一半以上的模具使用减面率10~21%的模具而进行拉丝加工,进一步在中途以200~600℃进行1至3次热处理,从而加工到直径20μm或直径18μm。在加工后,进行了热处理,使得最终断裂伸长率达到约5~15%。热处理方法为:一边连续地扫掠线一边进行,一边流动N2或者Ar气体一边进行。线的进给速度设为10~90m/分,热处理温度设为350~600℃,热处理时间设为1~10秒。关于实施例6、10、11、23、55、56、62、77的制造方法,在实施例11、56中,将热处理温度设为300℃以下的较低的温度,在实施例6、10、55、62、77中将热处理温度设为700℃以上的较高的温度。
(评价方法)
[元素的含量]
对于线中的各合金元素的含量,利用ICP发光光谱分析装置进行了分析。
[结晶粒径]
对于结晶粒径,用EBSD法进行了评价。对于EBSD测定数据的分析,利用了专用软件(TSL Solution制OIM Analysis等)。结晶粒径是对测定区域内所含有的结晶粒的当量直径(与结晶粒的面积相当的圆的直径)进行算术平均的结果。
[氧化铜的平均膜厚]
对于线表面的氧化铜的平均膜厚的测定,通过俄歇光谱分析进行深度分析,使用了在线表面的随机的位置的最低3处以上测定的氧化铜的膜厚的平均值。一边用Ar离子进行溅射一边在深度方向上测定,深度的单位以SiO2换算来表示。将氧化铜与金属铜的交界设为氧浓度为30质量%。此处的所谓氧浓度,使用了氧浓度相对于将Cu、氧、金属元素进行总计的浓度的比率。对于测定,使用SAM-670(PHI社制、FE型),将电子束的加速电压设为5kV,将测定区域设为10nA,以Ar离子溅射的加速电压为3kV、溅射速度为11nm/分实施了测定。将氧化铜的平均膜厚的测定结果记载在各表的“氧化铜平均膜厚”这一栏中。
[HAST]
对于高温高湿环境或高温环境下的球接合部的接合可靠性,制作接合可靠性评价用的样品,进行HAST评价,根据球接合部的接合寿命进行了判定。对在一般的金属框架上的Si基板上成膜厚度0.8μm的Al-1.0%Si-0.5%Cu的合金而形成的电极,使用市售的线接合机进行球接合,并利用市售的环氧树脂进行密封,从而制作了接合可靠性评价用的样品。对于球,一边以流量0.4~0.6L/min流动N2+5%H2气体一边形成,其大小设为φ33~34μm的范围。
对于HAST评价,使用不饱和型压力蒸煮器试验机,将制作了的接合可靠性评价用的样品暴露在温度130℃、相对湿度85%的高温高湿环境中,施加了7V的偏压。对于球接合部的接合寿命,每48小时实施球接合部的剪切试验,采用了剪切强度的值变成初始得到的剪切强度的1/2的时间。高温高湿试验后的剪切试验是在通过酸处理除去了树脂而使球接合部露出之后进行的。
HAST评价的剪切试验机使用了DAGE社制的试验机。剪切强度的值使用了随机选择的球接合部的10处的测定值的平均值。在上述的评价中,如果接合寿命小于96小时,则判断为实用上有问题并记为×记号,如果为96小时以上且小于144小时,则判断为尽管能够实用但略有问题并记为△记号,如果为144小时以上且小于192小时,则判断为实用上没有问题并记为○记号,如果为192小时以上则判断为优异并记为◎记号,并记载在各表的“HAST”这一栏中。仅×为不合格,除此以外为合格。
[FAB形状]
对于球部的球形成性(FAB形状)的评价,采样进行接合前的球并观察,判定了球表面的气泡的有无、本来正球的球的变形的有无。在发生了上述任一种的情况下,判断为不良。对于球的形成,为了抑制熔融工序中的氧化,而一边以流量0.5L/min吹送N2气体一边进行。球的直径设为线径的1.7倍。对1个条件观察了50个球。对于观察,使用了SEM。在球形成性的评价中,在发生了5个以上的不良的情况下,判断为有问题并标记×记号,如果不良为3~4个,则判断为尽管能够实用但略有问题并标记△记号,在不良为1~2个的情况下,判断为没有问题并标记○记号,在未发生不良的情况下,判断为优异并标记◎记号,并记载在各表的“FAB形状”这一栏中。仅×为不合格,除此以外为合格。
[楔接合性]
对于线接合部的楔接合性的评价,在引线框的导线部分上进行1000根的接合,并根据接合部的剥离的发生频度来进行了判定。引线框使用了实施了1~3μm的镀Ag的Fe-42原子%Ni合金引线框。在本评价中,设想了比通常更严格的接合条件,将接合台温度设定为比一般的设定温度区域低的150℃。在上述的评价中,在发生了11个以上的不良的情况下,判断为有问题并标记×记号,如果不良为6~10个,则判断为尽管能够实用但略有问题并标记△记号,在不良为1~5个的情况下,判断为没有问题并标记○记号,在未发生不良的情况下,判断为优异并标记◎记号,并记载在各表的“楔接合性”这一栏中。仅×为不合格,除此以外为合格。
[塌陷形状]
对于球接合部的塌陷形状的评价,从正上方观察进行了接合的球接合部,根据其正圆性进行了判定。接合对象使用了在Si基板上成膜了厚度1.0μm的Al-0.5%Cu的合金的电极。对于观察,使用光学显微镜,对1个条件观察了200处。将从正圆的偏离较大的椭圆状的球接合部、变形具有各向异性的球接合部判断为球接合部的塌陷形状不良。在上述的评价中,在发了6个以上的不良的情况下,判断为有问题并标记×记号,如果不良为4~5个,则判断为尽管能够实用但略有问题并标记△记号,在1~3个的情况下,判断为没有问题并标记○记号,在全部得到良好的正圆性的情况下,判断为特别优异并标记◎记号,并记载在各表的“塌陷形状”这一栏中。
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
(评价结果)
如表1、2所示,确认了:在第1元素的浓度合计为0.03~3.0质量%的实施例1~103所涉及的铜合金接合线中,在温度为130℃、相对湿度为85%的高温高湿环境下的HAST试验中,得到球接合部可靠性。
此外,线表面的氧化铜的平均膜厚为0.0005~0.02μm的范围的实施例1~103所涉及的接合线均为良好的HAST评价结果。
此外,在对于实施例的接合线中的、全模具数中的一半以上的模具将拉丝时的减面率设为10%以上、将拉丝后的热处理中的热处理温度设为600℃以下的较低的温度的实施例1~5、7~9、12~22、24~54、57~61、63~69、71~76、78~103所涉及的接合线中,垂直于接合线的线轴的方向的芯材截面中的平均结晶粒径(μm)为0.02×R+0.4以上、0.1×R+0.5以下的范围内(R为线的线径(μm))。在此,对第1元素的含量为0.8~1.0质%的实施例7~14的评价结果进行比较,在平均结晶粒径为上述范围内的接合线(实施例7~9、实施例12~14)中,与平均结晶粒径为上述范围外的接合线(实施例10,11)相比,楔接合性和球接合部的塌陷形状良好。根据该结果可知,当垂直于接合线的线轴的方向的芯材截面中的平均结晶粒径(μm)为0.02×R+0.4以上、0.1×R+0.5以下的范围内(R为线的线径(μm))时,楔接合性和球接合部的塌陷形状变得良好。
在实施例11中,因为将热处理温度设为300℃以下的较低的温度,所以平均结晶粒径小于优选范围的下限,楔接合性为“△”,从而成为稍微降低的结果。
在实施例10中,因为将热处理温度设为700℃以上的较高的温度,所以平均结晶粒径超过优选范围的上限,其结果,在实施例10中,塌陷形状为“△”,从而成为稍微降低的结果。
在含有2种以上的第1元素的实施例24~43所涉及的接合线中,与仅含有1种第1元素、且其含量为相同程度的实施例7~14所涉及的接合线相比,HAST试验的结果进一步良好。根据该结果可知,在含有2种以上的第1元素的接合线中,在温度为130℃、相对湿度为85%的高温高湿环境下的HAST试验中球接合部可靠性变得进一步良好。
在实施例所涉及的接合线中的、进一步含有分别为0.0001~0.050质量%的第2元素的实施例44~66所涉及的接合线中,球接合部的塌陷形状良好。
在实施例所涉及的接合线中的、进一步含有总计0.0005~0.5质量%的选自Ag、Au的至少1种以上的元素(第3元素)的实施例67~92所涉及的接合线中,球接合部的塌陷形状良好。
确认了:在实施例所涉及的接合线中的、进一步含有1.15质量%以下的Pd的实施例93~103所涉及的接合线中,在温度为130℃、相对湿度为85%的高温高湿环境下的HAST试验中,球接合部可靠性进一步变得良好。
在实施例所涉及的接合线中的、除了含有第1元素之外,还进一步含有分别为0.0001~0.050质量%的第2元素、及总计为0.0005~0.07质量%的选自Ag、Au的至少1种以上的元素(第3元素)的实施例75、76、84、85、90~92所涉及的接合线中,作为HAST评价结果,得到了楔接合性及球接合部的塌陷形状均良好这样的希望的结果。其中,在含有2种以上的第1元素的实施例75及76中,HAST评价结果特别良好。
此外,在实施例所涉及的接合线中的、除了含有第1元素之外,还进一步含有分别为0.0001~0.050质量%的第2元素、及1.15质量%以下的Pd的实施例98~99所涉及的接合线中,得到了HAST评价结果进一步良好、且FAB形状、楔接合性、及球接合部的塌陷形状良好这样的希望的结果。
另一方面,在比较例的接合线中的、第1元素合计浓度少于0.03质量%的比较例3、4的接合线中,在HAST试验中未得到球接合部可靠性,在第1元素合计浓度多于3质量%的比较例1、2、5、6的接合线中,FAB形状及楔接合性不良。
Claims (7)
1.一种半导体装置用铜合金接合线,其特征在于,
总计含有0.03质量%以上3质量%以下的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的至少1种以上的元素,其余部分由Cu和不可避免杂质构成。
2.如权利要求1所述的半导体装置用铜合金接合线,其特征在于,
当将线的线径设为R(μm)时,上述铜合金接合线的垂直于线轴的方向的芯材截面中的平均结晶粒径(μm)为:
0.02×R+0.4以上 (1a)
0.1×R+0.5以下 (1b)。
3.如权利要求1或2所述的半导体装置用铜合金接合线,其特征在于,
线表面的氧化铜的平均膜厚为0.0005~0.02μm的范围。
4.如权利要求1~3的任一项所述的半导体装置用铜合金接合线,其特征在于,
上述铜合金接合线进一步含有相对于线整体分别为0.0001~0.050质量%的选自Ti、B、P、Mg、Ca、La、As、Te、Se的至少1种以上的元素。
5.如权利要求1~4的任一项所述的半导体装置用铜合金接合线,其特征在于,
上述铜合金接合线进一步含有相对于线整体总计为0.0005~0.5质量%的选自Ag、Au的至少1种以上的元素。
6.如权利要求1~5的任一项所述的半导体装置用铜合金接合线,其特征在于,
上述铜合金接合线进一步含有1.15质量%以下的Pd。
7.如权利要求1~6的任一项所述的半导体装置用铜合金接合线,其特征在于,
上述铜合金接合线含有2种以上的选自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt的元素。
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