CN101363128B - Non-cyanogen type electrolytic gold plating bath for bump forming - Google Patents
Non-cyanogen type electrolytic gold plating bath for bump forming Download PDFInfo
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- CN101363128B CN101363128B CN2008101458670A CN200810145867A CN101363128B CN 101363128 B CN101363128 B CN 101363128B CN 2008101458670 A CN2008101458670 A CN 2008101458670A CN 200810145867 A CN200810145867 A CN 200810145867A CN 101363128 B CN101363128 B CN 101363128B
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- gold
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- plating bath
- gold plating
- golden
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- 239000010931 gold Substances 0.000 title claims abstract description 74
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 70
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000007747 plating Methods 0.000 title claims abstract description 63
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 22
- -1 sulfurous acid gold alkali salt Chemical class 0.000 claims abstract description 21
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 235000019252 potassium sulphite Nutrition 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- GKSYFVIEBZCLEQ-UHFFFAOYSA-N OS(O)=O.N.[Au+3] Chemical compound OS(O)=O.N.[Au+3] GKSYFVIEBZCLEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000007669 thermal treatment Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 238000000059 patterning Methods 0.000 claims description 5
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 3
- 229940117986 sulfobetaine Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 33
- 239000013543 active substance Substances 0.000 abstract 1
- 239000006172 buffering agent Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 29
- 239000000758 substrate Substances 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 235000013399 edible fruits Nutrition 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- KLBIUKJOZFWCLW-UHFFFAOYSA-N thallium(iii) nitrate Chemical compound [Tl+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KLBIUKJOZFWCLW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- OCNFLBCBOWEIRI-UHFFFAOYSA-N [K+].[Au+].S(O)(O)=O Chemical compound [K+].[Au+].S(O)(O)=O OCNFLBCBOWEIRI-UHFFFAOYSA-N 0.000 description 1
- RXNUQHQAZAAIDP-UHFFFAOYSA-N [Na+].[Au+].OS(O)=O Chemical compound [Na+].[Au+].OS(O)=O RXNUQHQAZAAIDP-UHFFFAOYSA-N 0.000 description 1
- JEOOVNWNJKBHRG-UHFFFAOYSA-N [Na+].[S--].[S--].[Au+3] Chemical compound [Na+].[S--].[S--].[Au+3] JEOOVNWNJKBHRG-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- BXBMHLIYMZRCNK-UHFFFAOYSA-H thallium(3+);trisulfate Chemical compound [Tl+3].[Tl+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BXBMHLIYMZRCNK-UHFFFAOYSA-H 0.000 description 1
- UFVDXEXHBVQKGB-UHFFFAOYSA-L thallous malonate Chemical compound [Tl+].[Tl+].[O-]C(=O)CC([O-])=O UFVDXEXHBVQKGB-UHFFFAOYSA-L 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
-
- 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
-
- 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
- H01L2924/01057—Lanthanum [La]
-
- 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
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Wire Bonding (AREA)
Abstract
The invention discloses non-cyanogens-like electrolysis golden electroplate liquid used for forming protrusion, in which comprises 5 g/L to 150 g/L of conductive salt consisting of sulfurous acid gold alkali salt or sulfurous acid gold ammonium as the gold source, a crystal regulator, and potassium sulfite, 1 mg/L to 6 g/L of polyalkylene glycol with molecular weight 200 to 6000 and/or 0.1 mg to 1 g/L of ampholytic active agent, water-soluble amine and/or buffering agent; after electroplate gold plating on a patterned wafer by used of the gold electroplate liquid of the invention, protrusion with film hardness at 50 Hv to 90 Hv, and surface height difference less than 1.8 microns is formed after heat treatment at 200 degrees centigrade to 400 degrees centigrade for 5 min.
Description
Technical field
The present invention relates to the electrolytic gold plating bath of the non-cyanogen class that is used to form projection of semiconductor wafer.Relate to form the non-cyanogen type electrolytic gold plating bath of projection in more detail with smooth surface and regulation hardness.The projection that forms is applicable to that the circuit of anisotropic conductive adhesive engages.
Background technology
For non-cyanogen type electrolytic gold plating bath, generally contain sulfurous acid gold alkali salt or sulfurous acid gold ammonium as golden salt.Known basic electroplate liquid is by these golden salt, with water-soluble amine as the gold complex stablizer, with Tl, Pb or the As compound of adjusting the trace of agent as the crystallization of electroplating tunicle, with so (special Willing 2005-286147 (claim), the special Willing 2005-145767 (claim)) that constitute as electrolytical S-WAT or sodium sulfate and buffer reagent.
The golden projection of using gold plating bath to form on semiconductor wafer, the electrode as IC, LSI is employed widely in recent years.
Fig. 3 is the sectional view of the golden projection of the prior art that forms on semiconductor wafer.
When on semiconductor wafer, forming golden projection, at first on semiconductor wafer 1, form aluminium (Al) electrode 2 of minor axis column by methods such as sputters.Semiconductor wafer 1 is to use the compound wafer of silicon wafer or GaAs etc.Be pre-formed the circuit layer 1 ' that contains unicircuit on the surface of wafer 1.Then, carry out wiring patternization with passive film 3.On the passive film 3, above Al electrode 2, form peristome 3a.
Then, titanium-tungsten (TiW) sputtered film 4 and lower process metal (UBM) layer that is made of golden sputtered film 56 form by sputter.The Al electrode 2 that UBM layer 6 covers passive film 3 and exposes its peristome 3a.On UBM layer 6, carry out mask with etchant resist 8.On the etchant resist above the Al electrode 28, form peristome 8a.Then, in the peristome 8a of etchant resist 8, form golden projection 7 with the plating of electrolysis gold.Then, remove etchant resist 8 and with the zone and the TiW sputtered film 4 of the golden sputtered film 5 beyond golden projection 7 covered parts.Qi Knot fruit, expose passive film 3, obtained forming the wafer of golden projection 7.
Formed the semiconductor wafer (that is, semi-conductor chip) of golden projection, in operation thereafter, be installed on the printed circuit board.During installation, the golden projection Zhi Inter that forms on electrode of substrate that forms wiring pattern on the printed circuit board and semiconductor wafer is connected.During connection, the wire bonding that uses lead-in wire is arranged and do not use the copulational protuberance of lead-in wire and the flip-chip combined techniques of electrode of substrate.
In recent years, in order to make the manufacturing process of semiconductor packages oversimplify, and positively engage, adopt the membranaceous anisotropic conductive adhesive of use on the flip-chip combined techniques mostly.Anisotropic conductive adhesive is dispersed in conducting particles in Resins, epoxy etc. and obtains.As conducting particles, use be covered the in turn conducting particles of nickel, gold of the surface of the particle on acrylic resin, form.
The shape of projection and hardness have very big influence to the connectivity of projection and substrate.The gold projection can also satisfy requirements such as shape with regulation, hardness except having excellent properties such as electronic conductivity, scale resistance.
Among Fig. 3,7 ' represents golden protrusion surface (with the junction surface of electrode of substrate).This surface 7 ' is not the surperficial parallel plane with wafer 1, but forms the outstanding convex in mediad top.Beyond above-mentioned, it is the situation of matrix shape that protrusion surface also has, and it is the situation of shape jaggy that periphery is also arranged.Conducting particles when the projection of these shape and substrate engage, in the binding agent drops on the recess and the periphery of protrusion surface easily.For this reason, conducting particles equably decentralized configuration at protrusion surface, and partially in the part on surface.Qi Knot fruit, bonding area reduce, golden projection and the other side's substrate engaging force weaken.At this moment, after assembling procedure is finished, be easy to generate owing to broken string, engage the bad electronic defects that produces.
In addition, when the hardness ratio conducting particles of projection hanged down, conducting particles can be embedded in projection Side.Conducting particles can not thermo-compressed between Qi Knot fruit, golden projection and the other side's substrate etc., can not keep engaging.
On the other hand, when projection hardness is too high, thereby because conducting particles is squeezed broken can't the joint, like this will be owing to broken string, the bad electronic defects that causes of joint.
Summary of the invention
Problem to be addressed by invention
As mentioned above, protrusion surface is uneven, forms the shape for lugs of convex, matrix, and perhaps projection is peripheral jagged, and the conducting particles that will make anisotropic conductive adhesive decentralized configuration equably and is configured in a part of surface at protrusion surface.Qi Knot really is the Jie He Mian Plot that has reduced by particle, has reduced joint Strong degree.
For this reason, when using anisotropic conductive adhesive to engage, when needing aforesaid suitable hardness, also need to form the planar gold projection that has high smoothness as the junction surface.
When using the electrolytic gold plating bath formation projection of prior art, golden projection hardness can not be manufactured needed hardness.Qi Knot really is, joint that the conducting particles that passes through anisotropic conductive adhesive that reach the defective that does not produce electronics carries out projection and electrode of substrate is suitable difficulty.
Therefore, the object of the present invention is to provide the non-cyanogen type electrolytic gold plating bath that is used to form projection of the golden projection of the hardness that can obtain being fit to the thermo-compressed by using anisotropic conductive adhesive and shape.
Solve the means of problem
The present inventor studies in order to address the above problem.Qi Knot really finds, by adjusting the aklylene glycol that adds to gold plating bath or the addition of amphoterics with regulation molecular weight, and can be in desirable scope with the Hardness Control of golden projection.And then, find can obtain the smooth projection in junction surface by using potassium sulfite and above-mentioned aklylene glycol Huo person both surfactivitys drug together as conduction salt.
In order to achieve the above object, the present invention puts down in writing as following.
(1) a kind of non-cyanogen type electrolytic gold plating bath that is used to form projection, it contains polyalkylene glycol 1mg/L～6g/L and/or amphoterics 0.1mg～1g/L, water-soluble amine and/or buffer reagent that agent, potassium sulfite 5～150g/L, molecular weight 200～6000 are adjusted in sulfurous acid gold alkali salt or sulfurous acid gold ammonium, crystallization.
(2) according to (1) described non-cyanogen type electrolytic gold plating bath that is used to form projection; amphoterics wherein, be from 2-alkyl-N-carboxyl methyl-N-hydroxyethyl imidazole trimethyl-glycine, dodecanamide propyl hydroxyl sulfo betaine, fatty acid amide CAB, and fatty acid acyl-N-propyloic-N-hydroxyethyl-ethylenediamine alkali salt select more than a kind or 2 kinds.
(3) according to (1) described non-cyanogen type electrolytic gold plating bath that is used to form projection, wherein crystallization adjustment agent is Tl compound, Pb compound or As compound, cooperates crystallization to adjust agent and makes metal concentration reach 0.1～100mg/L.
(4) a kind of projection formation method, its be at patterning wafer on use the non-cyanogen type electrolytic gold plating bath that is used to form projection of record in (1) to carry out the plating of electrolysis gold after, by more than 5 minutes 200～400 ℃ thermal treatment, formation is 50～90Hv by film hardness, and the difference of altitude on surface is the following projections of 1.8 μ m.
(5) a kind of syndeton, it is to use anisotropic conductive adhesive, with the electrode of substrate that has formed on the printed circuit board with substrate wiring pattern, with the golden projection connection structure connecting of the unicircuit that forms on the semiconductor wafer, wherein above-mentioned golden projection is 50～90Hv by film hardness.
Description of drawings
Fig. 1 is the sectional view that an example of the golden projection that gold plating bath of the present invention forms is used in expression.
Fig. 2 is that expression is with the sectional view that golden projection semi-conductor chip is installed in an example of state on the printed circuit board that has shown in Figure 1.
Fig. 3 is the sectional view that the golden projection that the gold plating bath of prior art forms is used in expression.
Among the figure, the 1st, semiconductor wafer, 1 ' is circuit layer, the 2nd, the Al electrode, the 3rd, passive film, 3a are the peristomes of passive film, the 4th, and TiW sputtered film, the 5th, golden sputtered film, the 6th, the UBM layer, the 7th, golden projection, 7 ' is the surface of golden projection, the 8th, etchant resist, 8a are the peristomes of etchant resist, the 10th, and printed circuit board, the 11st, hard substrate, the 12nd, substrate wiring pattern, the 14th, electrode of substrate, the 16th, semi-conductor chip, the 18th, packaged material, the 20th, anisotropic conductive adhesive.
The invention effect
Non-cyanogen type electrolytic gold plating bath of the present invention does not use S-WAT and uses potassium sulfite as conduction salt, and as containing amphoterics or polyalkylene glycol by composition.Thus, when on the compound semiconductor wafer of semiconductor silicon wafer, Ga/As etc., forming projection, can make projection smooth surface with excellent stiffness, no concave-convex, that constitute by electrolysis gold plating tunicle.
Particularly,, be engaged in the electroplate liquid, can control and have the projection hardness that is fit to the value arbitrarily of the scope of 50～90Hv of anisotropic conductive adhesive thermo-compressed with potassium sulfite by selecting molecular weight, the addition of polyalkylene glycol.
The hardness that has smooth crimping face and regulation by the golden projection of electroplate liquid formation of the present invention.For this reason, in semi-conductor manufacturing process, the anisotropic conductive film by using, anisotropic conductive can easily be carried out electrode engagement with the anisotropic conductive adhesive of adhesive film etc.And, produce disconnected Line, to engage bad ratio also few.
Use golden projection that electroplate liquid of the present invention forms not only on the junction surface, and also do not produce expansion, so can form the golden projection of the peristome shape of imitating etchant resist at the Side of the projection that contact with etchant resist face.Therefore, can form the Side face and above the corner post shape, the golden projection of polygonal column that constitute by the plane, the cylindric golden projection of homogeneous diameter.
Embodiment
Electrolytic gold plating bath of the present invention is the gold plating bath of non-cyanogen class, be by as the sulfurous acid of Jin Yuan gold alkali salt or sulfurous acid gold ammonium, water-soluble amine as the stablizer of gold complex salt, agent is adjusted in the crystallization of trace, in the electroplate liquid that buffer reagent constitutes, contain electrolytic gold plating bath as potassium sulfite, polyalkylene glycol and/or the amphoterics of conduction salt.Do not contain S-WAT in fact as conduction salt.
Below, the essential composition to electrolytic gold plating bath of the present invention describes each composition respectively.
(1) sulfurous acid gold alkali salt, sulfurous acid gold ammonium (Jin Yuan)
As the sulfurous acid gold alkali salt that uses among the present invention, can use known sulfurous acid gold alkali salt without restriction.As sulfurous acid gold alkali salt, for example can enumerate sulfurous acid gold (I) sodium, sulfurous acid gold (I) potassium etc.Can use these individually a kind, perhaps also can and with wherein more than 2 kinds.
As Jin Yuan, can use above-mentioned sulfurous acid gold alkali salt or sulfurous acid gold ammonium in the electrolytic gold plating bath of the present invention, but its proportional quantity, in gold amount normally 1～20g/L, 8～15g/L preferably.During the proportional quantity of sulfurous acid gold alkali salt or sulfurous acid gold ammonium is not enough 1g/L, the thickness of electroplating tunicle can produce inhomogeneous.When surpassing 20g/L, though electroplate Mei You Inter such as the characteristic topic of tunicle, manufacturing cost uprises becomes burden economically.
(2) water-soluble amine (stablizer)
As water-soluble amine, can use carbonatoms is more than 2, and preferably using carbonatoms is 2～6 diamines, for example can enumerate 1,1,1 etc.Can use these individually a kind, also can and with wherein more than 2 kinds.
The proportional quantity of water-soluble amine, normally 0.1～30g/L, preferably 1～12g/L.When the proportional quantity of water-soluble amine surpasses 30g/L,, plate tunicle densification exceedingly on the other hand, produce the connectivity condition of poor sometimes though the stability of gold complex salt can increase.During deficiency 0.1g/L, limit current density descends and causes the situation of excessive plating (blackening is arranged) sometimes.
(3) Tl compound, Pb compound, As compound (crystallization adjustment agent)
Adjust agent as the crystallization of using in the electrolytic gold plating bath of the present invention, can enumerate for example Tl compound of formic acid thallium, thallous malonate, thallic sulfate, thallium trinitrate (TTN) etc.; The Pb compound of Ning Meng Suan , Xiao Suan , Lian Wan Huang Suan etc.; The As compound of white arsenic etc.These Tl compound, Pb compound, As compound can use a kind separately, also can be used in combination wherein more than 2 kinds.
The proportional quantity that agent is adjusted in crystallization can carry out suitable setting in the scope of not damaging purpose of the present invention, but as metal concentration 0.1～100mg/L normally, preferably 0.5～50mg/L, 3～25mg/L more preferably.When the proportional quantity deficiency 0.1mg/L of agent is adjusted in crystallization, the stability of paying property of coating, electroplate liquid and weather resistance meeting variation, the composition of electroplate liquid can decompose sometimes.When surpassing 100mg/L, may produce the deterioration of paying property of coating and the outward appearance spot of plating tunicle.
(4) potassium sulfite (conduction salt)
In the electrolytic gold plating bath of the present invention, use potassium sulfite as conduction salt.
As the proportional quantity of the potassium sulfite in the electrolytic gold plating bath of the present invention, in the scope of not damaging purpose of the present invention, can suitably set, following proportional quantity is proper.
The proportional quantity of potassium sulfite is generally 5～150g/L, preferably 10～150g/L, more preferably 50～100g/L, 60～90g/L most preferably.During the proportional quantity of potassium sulfite is not enough 5g/L, thereby the expansion that can not suppress shape for lugs fully can not be made into even shape with protrusion surface.And, paying property of coating and liquid stabilising variation, the decomposition that produces electroplate liquid sometimes.When surpassing 150g/L, limit current density descends becomes excessive plating sometimes.
Do not contain sodium salt in the electroplate liquid of the present invention in fact as the S-WAT that conducts salt, sodium sulfate etc.Contained sodium is only limited to from the gold sodium sulfide as Jin Yuan in the electroplate liquid.
(5) buffer reagent
As employed buffer reagent among the present invention, so long as employed just passable in the common electrolytic gold plating bath, there is no particular limitation to this.For example can use, the organic acid of the inorganic acid salt of phosphoric acid salt, borate etc., Citrate trianion, phthalic acid salt, ethylene dinitrilotetra-acetic acid salt etc. (polyvalent carboxylic acid of 2 to 5 valencys, hydroxycarboxylic acid) salt etc., can use these individually a kind, also can and with wherein more than 2 kinds.
Proportional quantity as buffer reagent in the non-cyanogen type electrolytic gold plating bath of the present invention is generally 1～30g/L, preferably 2～15g/L, 2～10g/L more preferably.During the proportional quantity of buffer reagent is not enough 1g/L, because pH descends liquid stabilising variation, the decomposition that produces the electroplate liquid composition sometimes.When surpassing 30g/L, limit current density descends, and becomes excessive plating sometimes.
(6) polyalkylene glycol, amphoterics
As the polyalkylene glycol that is engaged in the non-cyanogen type electrolytic gold plating bath of the present invention, can enumerate polyoxyethylene glycol, polypropylene glycol etc.
As amphoterics, the trimethyl-glycine that can enumerate 2-alkyl-N-carboxyl methyl-N-hydroxyethyl imidazole trimethyl-glycine, dodecanamide propyl hydroxyl sulfo betaine, fatty acid amide CAB etc. is an amphoterics; The aminocarboxylate of fatty acid acyl-N-propyloic-N-hydroxyethyl-ethylenediamine alkali salt etc. is an amphoterics; Imidazolidine derivatives is an amphoterics etc.
The proportional quantity of polyalkylene glycol is 1mg/L～6g/L, preferably 20～3000mg/L, 100～1000mg/L more preferably.On the other hand, the proportional quantity of amphoterics, normally 0.1mg/L～1g/L, preferably 5～500mg/L, 10～300mg/L more preferably.When the proportional quantity of polyalkylene glycol and amphoterics all is lower than above-mentioned scope, then the projection after the thermal treatment by the not enough 50Hv of film hardness, and then the surface of projection can not be made into smooth shape.When surpassing above-mentioned scope, the projection after the thermal treatment be to obtain being fit to the hardness that engages more than the 90Hv by film hardness.
Polyalkylene glycol and amphoterics also can only be to use wherein a kind of, also can two kinds and use.And during with two kinds, both proportional quantities are in above-mentioned each scope, the adjusting suitable according to purpose.
When using polyalkylene glycol, be fit to the 50～90Hv of Anisotropically conductive by film hardness, so use molecular weight 200～6000, preferably 400～2000, more preferably 400～1000 with the joint of adhesive film for what make golden projection after the thermal treatment.Molecular weight surpasses at 6000 o'clock, is reached 50～90Hv by film hardness in order to make after the thermal treatment, proportional quantity need be controlled at the extremely low concentration of not enough 1mg/L.The electroplate liquid of the proportional quantity of such lower concentration is very difficult in the concentration management.
By regulating the proportional quantity of the polyalkylene glycol of molecular weight below 6000, can will in the scope of 50～90Hv, adjust to desirable value by the hardness of electroplating the tunicle that forms.During the situation of low-molecular-weight polyalkylene glycol by increasing proportional quantity, during the high-molecular weight situation by reducing proportional quantity, can obtain 50～90Hv by film hardness.For any molecular weight, can will be improved by film hardness by increasing proportional quantity, obtain near the higher hardness of the ratio of 90Hv.
For example, with after the thermal treatment be made into 70Hv by film hardness the time, be controlled at 1mg/L～6g/L by proportional quantity with the polyalkylene glycol of molecular weight below 6000, preferably 20～3000mg/L just can achieve the goal.And then the proportional quantity of the amphoterics of this moment is 10～300mg/L preferably.
In general, because the increase of the proportional quantity of polyalkylene glycol or amphoterics, because can being reduced of causing of thermal treatment by film hardness decline.And, cooperating potassium sulfite, when mismatching the situation of polyalkylene glycol or amphoterics, the difference of altitude of protrusion surface can not fully diminish.Have only to add two kinds of potassium sulfite and polyalkylene glycol or amphotericses simultaneously, just can satisfy the difference of altitude of protrusion surface simultaneously and by film hardness two sides' expected value.
In the non-cyanogen type electrolytic gold plating bath of the present invention, in the scope of not damaging purpose of the present invention, also can suitably use pH to adjust other compositions of agent etc.
Adjust agent as pH, for example can enumerate sulfuric acid as acid, sulfurous sour water, phosphoric acid etc., as the potassium hydroxide of alkali, ammoniacal liquor etc.
Use non-cyanogen type electrolytic gold plating bath of the present invention, when on semiconductor wafer, forming projection, can electroplate just passable according to ordinary method by plating.For example, as the Ti-W sputtered film of UBM layer, carry out mask with mask material on the wafer of Au sputtered film of Xing Chenging etc. thereon.Wafer as plated body carried out electrolysis gold plating thereafter.Then have and mask material is dissolved in method of removing in the solvent etc.After removing mask material, remove not by the part of the golden projection lining of UBM layer, carry out the thermal treatment of wafer by corrosion etc.
For the mask drug, can use phenolic aldehyde is eurymeric light etchant resist.For example as product sold on the market, can enumerate LA-900, HA-900 (more than be that Tokyo Applied Chemistry Industrial Co., Ltd. makes) etc.
Normally 40～70 ℃ of electroplating temperatures, preferably 50～65 ℃.During scope that the temperature departure of electroplate liquid is 40～70 ℃, the situation that may exist the plating tunicle to be difficult to separate out, the electroplate liquid situation that instability generation electroplate liquid composition decomposes that becomes.
The setting current density of using in the plating is that the condition of the composition, temperature according to electroplate liquid etc. is different and be different in suitable scope, so can't lump together.At gold concentration is 8～15g/L, following time of condition of temperature of electroplating solution of 60 ℃, normally following, the 0.2～1.2A/dm2 preferably of 2.0A/dm2.When the current density of setting departs from above-mentioned scope, can produce the operability variation, electroplate the tunicle outward appearance, electroplate by membrane property and produce unusual situation, thereby or produce the situation that electroplate liquid instability electroplate liquid composition decomposes significantly.
As the pH value of non-cyanogen type electrolytic gold plating bath of the present invention, normally more than 7.0, preferably 7.2～10.0.During the pH value less than 7.0 of non-cyanogen type electrolytic gold plating bath, thereby unstable significantly the generation sometimes of electroplate liquid decomposed.The pH value surpasses at 10.0 o'clock on the other hand, and then mask material dissolving can not form the golden projection of hope etc. sometimes.
The thermal treatment temp of gold projection is 200～400 ℃, preferably 200～300 ℃.Re Chu Li Time Inter is more than 5 minutes, preferably 30～60 minutes.Use meticulous thermostat container etc. that chamber interior Bao under design temperature is held Yi during thermal treatment and Ding Time Inter.
Non-cyanogen type electrolytic gold plating bath of the present invention by to Jin Yuan and constitute other the Fill of composition of electroplate liquid and fill management, can use more than 2 circulations (when the gold amount in the electroplate liquid all consumes in plating as 1 circulation).
Non-cyanogen type electrolytic gold plating bath of the present invention, but for matrix so long as metallized conducting then can not be chosen as plated body.Use phenolic aldehyde be eurymeric light etchant resist as mask material, be particularly suitable on compound wafer such as Ga/As wafer on the silicon wafer of patterning, forming projection.
Fig. 1 is that gold plating bath of the present invention is used in expression, forms the sectional view of an example of golden projection on semiconductor wafer.Among Fig. 1, the 1st, semiconductor wafer, 1 ' is the circuit layer that contains unicircuit that forms on the surface of semiconductor wafer, the 2nd, the Al electrode, the 3rd, passive film, 3 a are peristomes of passive film, the 4th, and the TiW sputtered film, the 5th, golden sputtered film, the 6th, the UBM layer that TiW sputtered film 4 and golden sputtered film 5 constitute, the 7th, golden projection, 7 ' is the surface of golden projection 7, the 8th, etchant resist, 8a are the peristomes of etchant resist.The surface 7 ' of gold projection is to form smooth face, difference of altitude around central part 7 ' a and etchant resist are contacted between the 7 ' b of end (from wafer 1 De Ju From poor) is in the 1.8 μ m, preferably 1.7 μ m with interior, more preferably 1.6 μ m with interior, most preferably in the 1.5 μ m.
Fig. 2 represents the semi-conductor chip of the golden projection of formation shown in Figure, 1 is installed in the sectional view of De Zhuan on the printed circuit board.The part identical with Fig., 1 used identical symbol, omits its explanation.
On the hard substrate 11 of printed circuit board 10, formed substrate wiring pattern 12 with the conductive material of copper etc.On substrate wiring pattern 12, formed electrode of substrate 14 with the conductive material of gold etc.On the other hand, be installed in parallel on the semi-conductor chip 16 on the substrate 10, forming golden projection 7 facing to electrode of substrate 14 with printed circuit board 10.Aforesaid substrate electrode 14 and golden projection 7 usefulness anisotropic conductive adhesive 20 are bonded together.Between hard substrate 11 and the semiconductor wafer 1, encapsulate with packaged material 18.
The material of hard substrate 11 so long as can use just passable on the hard printed circuit board, has no particular limits this, for example can enumerate glass fiber reinforced epoxy resin, pottery etc.As packaged material 18, the known resin that uses in the time of can using the encapsulation of common semi-conductor chip.In the formation of hard substrate 11 upper substrate wiring patterns 10, electrode of substrate 14, can wait by the burn into Dao Dian Tu Liao De Tu cloth of evaporation, plating, metallic film and carry out.
The method of semi-conductor chip 16 is installed on printed circuit board 10, and available following method is carried out.At first, above electrode of substrate 14, face toward the position of the determining positions semi-conductor chip 16 of golden projection 7, sandwich membranaceous anisotropic conductive adhesive 20, semi-conductor chip 16 is loaded on the printed circuit board 10.Then, by anisotropic conductive adhesive 20 with golden projection 7 and electrode of substrate 14 thermo-compressed.By semi-conductor chip 16 is installed on printed circuit board 10, the electrode of substrate 14 as formation on the golden projection 7 of the electrode of the unicircuit that forms circuit layer 1 ' in and the substrate wiring pattern 12 is joined together by anisotropic conductive adhesive 20.
Embodiment
According to the represented cooperation in table 1～5, the preparation non-cyanogen type electrolytic gold plating bath.The unit of the cooperation concentration of each raw material is g/L when not specifying.But Na3Au (SO3) 2, sulfurous acid gold ammonium are the concentration of expression Au amount.
As plated body, (it is golden sputtered film/TiW/SiO2) that the matrix section is formed to the silicon wafer with projection peristome that to use phenolic aldehyde be eurymeric light etchant resist patterning.In the preparation of 1L non-cyanogen type electrolytic gold plating bath in flood plated body, imposing energising and forming gold plating tunicle with 15 μ m thickness.In addition, the current efficiency of non-cyanogen type electrolytic gold plating bath, under the constant electroplating manipulation condition, normally 100%.
After formation has the tunicle of regulation thickness, remove mask material, for shape, the electroplate liquid stability of the projection that forms, electroplate the tunicle outward appearance, be that the corrodibility of etching reagent is estimated according to following method and standard by film hardness (not after thermal treatment and the 300 ℃ of thermal treatment in 30 minutes), Au sputtered film by iodine.Its result is illustrated in table 1～5 together.
(difference of altitude of protrusion surface (μ m))
Represented as Fig. 1, using phenolic aldehyde on silicon wafer 1 is eurymeric light etchant resist 8, and carrying out patterning, to obtain having long limit be that 80～20 μ m, minor face are 80～20 μ m De Long square aperture portions.After using electrolytic gold plating bath to implement to electroplate, be eurymeric light etchant resist with methylethylketone dissolving phenolic aldehyde.For the projection that obtains, what the laser microscope VK-9710 that makes with KEYENCE society will measure vertex above the projection and top outer Side descends difference between the point as difference of altitude, as the finger Standard of smoothness most.In addition, the difference of altitude of trying to achieve in the projection plating purposes is below the 3 μ m usually, preferably below the 2 μ m, more preferably below the 1.5 μ m.
(electroplate liquid stability)
The state of the electroplate liquid of observation after plated body is implemented to electroplate is estimated according to following standard.
Decompose: the composition in the electroplate liquid decomposes.
*: the degree that the precipitation of gold can with the naked eye be judged in the electroplate liquid.
△: just see the precipitation that trace gold is arranged in the electroplate liquid.Can observed degree after filtering with 0.2 μ m membrane filter.
Zero: the precipitation of in electroplate liquid, not observing gold.
(electroplating the tunicle outward appearance)
The surperficial tunicle outward appearance of the golden projection that observation forms on plated body is estimated according to following standard.
*: tone is red, can see that dendroid is separated out, spot, or takes place excessively to electroplate.
△: do not separate out gloss appearance unusually.
Zero: tone is lemon yellow, tarnish～semilustrous uniform outer appearance.
(by film hardness (DPH; Hv))
Use the specific protruding part that forms on the plated body, with the DPH instrumentation fixed its by film hardness (not after thermal treatment and the 300 ℃ of thermal treatment in 30 minutes).As the characteristic that obtains in the projection of middle hardness purposes, after the annealing is about 70Hv by film hardness.Ci Wai ， Measuring fixed condition Shi keeps Measuring level pressure the condition in 10 seconds under the 25gf load.
(iodine of Au sputtered film is the corrodibility of etching reagent)
The iodine that stirs ten minutes at normal temperatures is dipping 90 seconds of plated body in the etching reagent, be the rinsing liquid washing with alcohol after, spraying ethanol drying machine drying.Afterwards, use metalloscope, observe the Biao Mian Zhuan of the full projection that forms on the plated body, estimate according to following standard with 50～200 times multiplying powers.
*: on the surface of the projection more than 50%, observe spot.
△: the surface observation that is only limited to a part of regional projection is to spot.
Zero: on the surface of the full projection on the plated body, do not observe spot.
(comprehensive evaluation)
Based on above-mentioned each evaluation result, estimate with following judgement criteria.
*: in the last commentary valency Knot fruit of the non-cyanogen type electrolytic gold plating bath after plating tunicle (golden projection) and electroplating processes, contain bad result about the gold that forms.
△: in above-mentioned evaluation result, contain roughly good and the Hao De Knot fruit of a part of Bu about the gold plating tunicle (golden projection) that forms and the non-cyanogen type electrolytic gold plating bath after the electroplating processes.
Zero: in the last commentary valency Knot fruit of the non-cyanogen type electrolytic gold plating bath after plating tunicle (golden projection) and electroplating processes, all be good result about the gold that forms.
Table 1
Table 2
Table 3
Table 4
Table 5
Polyoxyethylene glycol A: molecular-weight average 400
Polyoxyethylene glycol B: molecular-weight average 1000
Polyoxyethylene glycol C: molecular-weight average 6000
Amphoterics A: NOF Corp makes, ニ Star サ Application ア ノ Application BDL (carboxybetaine system)
Amphoterics B: Kao Corp makes, ア Application ヒ ト one Le 20YB (carboxybetaine system)
By comparative example, comparative example following thing has been described significantly.
(1) in principle, potassium sulfite can reduce the difference of altitude of protrusion surface effectively.The difference of altitude 1.01～1.56 that contains the embodiment 1～20 of potassium sulfite compares with the difference of altitude 1.85～3.11 of the comparative example that contains S-WAT 2～12 that replaces potassium sulfite, and the difference of altitude of protrusion surface is significantly less.
(2) in principle, polyalkylene glycol, the decline by film hardness of amphoterics after reducing by 300 ℃ of thermal treatments are very resultful.The embodiment 1～20 that contains polyalkylene glycol or amphoterics is appropriate (50～90Hv) by film hardness after 300 ℃ of thermal treatment.In contrast, the hardness that does not contain the comparative example 1,2 of polyalkylene glycol and amphoterics has been reduced to 45Hv, 43Hv.
(3), when just adding potassium sulfite, the difference of altitude of protrusion surface can not fully reduce.Although comparative example 1 adds the potassium sulfite with embodiment 1～20 same amount, difference of altitude is big (1.83) still.By in potassium sulfite, adding polyalkylene glycol or amphoterics, just make difference of altitude become (embodiment 1～20) below 1.56.
Claims (2)
1. non-cyanogen type electrolytic gold plating bath that is used to form projection; it is characterized in that it contains sulfurous acid gold alkali salt or sulfurous acid gold ammonium; by the Tl compound; the Pb compound; or agent is adjusted in the crystallization that the As compound is formed; the conduction salt 10～150g/L that constitutes by potassium sulfite only; polyalkylene glycol 1mg/L～the 6g/L of molecular weight 200～6000 and/or from 2-alkyl-N-carboxyl methyl-N-hydroxyethyl imidazole trimethyl-glycine; the dodecanamide propyl hydroxyl sulfo betaine; the fatty acid amide CAB; and the amphoterics 0.1mg～1g/L more than a kind or 2 kinds that selects in fatty acid acyl-N-propyloic-N-hydroxyethyl-ethylenediamine alkali salt; water-soluble amine and/or buffer reagent.
2. method that forms projection, it is characterized in that, its be at patterning wafer on use the non-cyanogen type electrolytic gold plating bath that is used to form projection of record in the claim 1, after having carried out the plating of electrolysis gold, by more than 5 minutes 200～400 ℃ thermal treatment, formation is 50～90Hv by film hardness, and the difference of altitude on surface is the following projections of 1.8 μ m.
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| JP5442400B2 (en) * | 2009-11-13 | 2014-03-12 | ルネサスエレクトロニクス株式会社 | Manufacturing method of semiconductor integrated circuit device |
| CN102753732A (en) * | 2010-03-26 | 2012-10-24 | 美泰乐科技(日本)股份有限公司 | Cyanide based electrolytic gold plating solution and plating method using same |
| JP5620798B2 (en) * | 2010-12-01 | 2014-11-05 | メタローテクノロジーズジャパン株式会社 | Non-cyan electrolytic gold plating bath for gold bump formation and gold bump formation method |
| CN102254891A (en) * | 2011-08-01 | 2011-11-23 | 三星半导体(中国)研究开发有限公司 | Flip chip packaging structure and manufacturing method thereof |
| JP6011074B2 (en) * | 2012-01-20 | 2016-10-19 | 富士通株式会社 | Electronic device manufacturing method and electronic device manufacturing apparatus |
| CN103290440B (en) * | 2012-02-22 | 2016-12-14 | 美泰乐科技(日本)股份有限公司 | Au bump formation non-cyanogen type electrolytic gold plating bath and au bump forming method |
| KR101464343B1 (en) * | 2013-04-02 | 2014-11-28 | 한밭대학교 산학협력단 | Non cyanide gold plating bath for bump and preparation method of bump |
| JP6393526B2 (en) * | 2014-06-11 | 2018-09-19 | メタローテクノロジーズジャパン株式会社 | Cyan-based electrolytic gold plating bath and bump forming method using the same |
| JP6659247B2 (en) | 2015-06-16 | 2020-03-04 | デクセリアルズ株式会社 | Connecting body, manufacturing method of connecting body, inspection method |
| CN105401180A (en) * | 2015-12-23 | 2016-03-16 | 苏州市金星工艺镀饰有限公司 | Electroplating liquid of wear-resistant gold-plated film and electroplating method thereof |
| CN105401181A (en) * | 2015-12-23 | 2016-03-16 | 苏州市金星工艺镀饰有限公司 | Electroplating method of environmentally-friendly cyanide-free gold-plating electroplating fluid |
| CN113913879B (en) * | 2021-09-30 | 2022-08-09 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electrogilding solution, use thereof, method for producing gold bumps by electrogilding, gold bumps and electronic components |
| JP7017664B1 (en) * | 2021-11-11 | 2022-02-08 | 松田産業株式会社 | Nosian electrolytic gold plating solution |
| KR102477921B1 (en) * | 2021-11-11 | 2022-12-14 | 마츠다 산교 가부시끼가이샤 | Non-annual Electrolytic Gold Plating Solution |
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| JP2006322037A (en) * | 2005-05-18 | 2006-11-30 | Electroplating Eng Of Japan Co | Gold-plating solution |
| JP4713290B2 (en) * | 2005-09-30 | 2011-06-29 | エヌ・イーケムキャット株式会社 | Forming method of gold bump or gold wiring |
| JP2009062584A (en) * | 2007-09-06 | 2009-03-26 | Ne Chemcat Corp | Cyanide-free electrolytic gold plating bath for bump formation, and method for forming bump |
| JP2009071093A (en) * | 2007-09-14 | 2009-04-02 | Ne Chemcat Corp | Bump and bump forming method |
-
2008
- 2008-07-30 JP JP2008195566A patent/JP5336785B2/en active Active
- 2008-08-05 TW TW097129689A patent/TWI477660B/en active
- 2008-08-06 KR KR1020080076964A patent/KR20090014992A/en active Search and Examination
- 2008-08-07 CN CN2008101458670A patent/CN101363128B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944716A (en) * | 2005-09-30 | 2007-04-11 | 恩伊凯慕凯特股份有限公司 | Non-cyanogen type electrolytic gold plating bath for bump forming |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200925336A (en) | 2009-06-16 |
| TWI477660B (en) | 2015-03-21 |
| JP5336785B2 (en) | 2013-11-06 |
| KR20090014992A (en) | 2009-02-11 |
| JP2009057631A (en) | 2009-03-19 |
| CN101363128A (en) | 2009-02-11 |
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