TWI829653B - Electroless palladium plating solution and electroless palladium plating film - Google Patents
Electroless palladium plating solution and electroless palladium plating film Download PDFInfo
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- TWI829653B TWI829653B TW107135158A TW107135158A TWI829653B TW I829653 B TWI829653 B TW I829653B TW 107135158 A TW107135158 A TW 107135158A TW 107135158 A TW107135158 A TW 107135158A TW I829653 B TWI829653 B TW I829653B
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- Taiwan
- Prior art keywords
- plating
- electroless
- plating film
- compound
- plating solution
- Prior art date
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- 238000007747 plating Methods 0.000 title claims abstract description 170
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 27
- -1 hypophosphite compound Chemical class 0.000 claims abstract description 45
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910000085 borane Inorganic materials 0.000 claims abstract description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- AQBOUNVXZQRXNP-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.N.N.Cl[Pd]Cl AQBOUNVXZQRXNP-UHFFFAOYSA-L 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 53
- 239000010931 gold Substances 0.000 description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000006104 solid solution Substances 0.000 description 14
- 229910052737 gold Inorganic materials 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001639 boron compounds Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 102100023033 Cyclic AMP-dependent transcription factor ATF-2 Human genes 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101000974934 Homo sapiens Cyclic AMP-dependent transcription factor ATF-2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
Abstract
本發明之課題為提供一種無電解鈀鍍敷液，其所得到的Pd鍍敷被膜係可構成即使是在熱歷程之後亦具有優異的導線接合性的鍍敷被膜，本發明的無電解鈀鍍敷液具有下述之要旨，含有鈀化合物、選自由次亞磷酸化合物及亞磷酸化合物所成之群中之至少1種、選自由胺硼烷化合物及氫硼化合物所成之群中之至少1種與錯合劑。An object of the present invention is to provide an electroless palladium plating solution, the Pd plating film obtained by which can constitute a plating film having excellent wire bonding properties even after a thermal history. The electroless palladium plating solution of the present invention The dressing solution has the following gist: it contains a palladium compound, at least one selected from the group consisting of a hypophosphite compound and a phosphorous acid compound, and at least one selected from the group consisting of an amine borane compound and a hydrogen borane compound. Seed and miscellaneous mixture.
Description
本發明為關於無電解鈀鍍敷液及無電解鈀鍍敷被膜。The present invention relates to an electroless palladium plating solution and an electroless palladium plating film.
在電子產業領域中作為印刷基板的電路、IC封裝體的安裝部分或端子部分等的表面處理法，已廣泛使用可賦予優異的焊錫接合性及導線接合性等的鍍敷被膜特性的效果的無電解鎳/無電解鈀/置換金法(Electroless Nickel Electroless Palladium Immersion Gold：ENEPIG)，廣泛使用了藉由ENEPIG製程來依序實施無電解鎳鍍敷被膜(以下有稱為「Ni鍍敷被膜」之情形)、無電解鈀鍍敷被膜(以下有稱為「Pd鍍敷被膜」之情形)、置換金鍍敷被膜(以下有稱為「Au鍍敷被膜」之情形)而成的鍍敷被膜(以下有稱為「無電解Ni/Pd/Au鍍敷被膜」之情形)。In the electronics industry, stainless steel is widely used as a surface treatment method for circuits on printed circuit boards, mounting portions or terminal portions of IC packages, etc., which have the effect of imparting plating film properties such as excellent solder bonding properties and wire bonding properties. The electrolytic nickel/electroless palladium/replacement gold method (Electroless Nickel Electroless Palladium Immersion Gold: ENEPIG) widely uses the ENEPIG process to sequentially implement electroless nickel plating films (hereinafter referred to as "Ni plating films"). case), an electroless palladium plating film (hereinafter referred to as "Pd plating film"), a plating film that replaces a gold plating film (hereinafter referred to as "Au plating film") ( Hereinafter, it is called "electrolytic Ni/Pd/Au plating film").
近年，為了對應隨著電子零件的小型化、高密度化所要求的鍍敷被膜特性，例如，提案了以改良無電解鈀鍍敷液(以下有稱為「無電解Pd鍍敷液」之情形)來改良鍍敷被膜特性之技術。In recent years, in order to cope with the plating film characteristics required as electronic components become smaller and higher in density, for example, improvements in electroless palladium plating solutions (hereinafter referred to as "electrolytic Pd plating solutions") have been proposed. ) to improve the properties of plating films.
例如，專利文獻1提案著一種無電解Pd鍍敷液，其係藉由使用鉍或鉍化合物取代硫磺化合物來作為穩定化劑，而可得到和使用硫磺化合物之情形為同等程度的鍍敷浴穩定性為高、且耐蝕性、焊錫接合性、導線接合性為優異的被膜。 [先前技術文獻] [專利文獻]For example, Patent Document 1 proposes an electroless Pd plating solution that uses bismuth or a bismuth compound as a stabilizer instead of a sulfur compound, thereby achieving the same level of plating bath stability as when a sulfur compound is used. A coating with high corrosion resistance, solder bonding properties, and wire bonding properties. [Prior technical literature] [Patent Document]
[專利文獻1]日本專利第4596553號[Patent Document 1] Japanese Patent No. 4596553
[發明所欲解決之課題][Problem to be solved by the invention]
已廣泛使用的無電解Ni/Pd/Au鍍敷被膜具有下述般之問題:在被暴露於迴焊處理等的高溫熱歷程之前，展現出優異的導線接合性，但在高溫熱歷程之後，導線接合性會顯著地降低。The electroless Ni/Pd/Au plating film that has been widely used has the following problem: it exhibits excellent wire bonding properties before being exposed to high-temperature thermal history such as reflow processing, but it fails after high-temperature thermal history. After that, the wire bondability will be significantly reduced.
本發明為著眼於如上述般情事而完成之發明，本發明之目的為提供一種無電解Pd鍍敷液及Pd鍍敷被膜，其所得到的Pd鍍敷被膜係可構成即使是在高溫熱歷程之後亦具有優異的導線接合性的鍍敷被膜。 [解決課題之手段]The present invention has been accomplished in view of the above-mentioned circumstances, and an object of the present invention is to provide an electroless Pd plating solution and a Pd plating film. The resulting Pd plating film can form a structure even under high-temperature heat. A plating film with excellent wire bonding properties even after the process. [Means to solve the problem]
解決上述課題的本發明的無電解鈀鍍敷液具有下述之要旨，含有鈀化合物、選自由次亞磷酸化合物及亞磷酸化合物所成之群中之至少1種、選自由胺硼烷化合物及氫硼化合物所成之群中之至少1種與錯合劑。The electroless palladium plating solution of the present invention that solves the above-mentioned problems has the following gist: it contains a palladium compound, at least one selected from the group consisting of a hypophosphite compound and a phosphorous acid compound, an amine borane compound, and a palladium plating solution. At least one of the group consisting of hydrogen and boron compounds and a complexing agent.
作為本發明的無電解鈀鍍敷液的較佳實施樣態，亦包含任意組合下述要件而成之構成。 (i)上述胺硼烷化合物為選自由二甲基胺硼烷及三甲基胺硼烷所成之群中之至少1種； (ii)上述氫硼化合物為硼氫化鹽； (iii)上述錯合劑為選自由氨及胺化合物所成之群中之至少1種。As a preferred embodiment of the electroless palladium plating solution of the present invention, a structure in which the following requirements are arbitrarily combined is also included. (i) The above-mentioned amine borane compound is at least one selected from the group consisting of dimethylamine borane and trimethylamine borane; (ii) The above-mentioned borohydride compound is a borohydride salt; (iii) The above complexing agent is at least one selected from the group consisting of ammonia and amine compounds.
又，本發明亦包含一種無電解鈀鍍敷被膜，其特徵在於含有磷及硼。於該無電解鈀鍍敷被膜的表面進一步具有無電解金鍍敷被膜之構成，亦屬於無電解鈀鍍敷被膜的較佳實施樣態。Furthermore, the present invention also includes an electroless palladium plating film characterized by containing phosphorus and boron. The surface of the electroless palladium plating film is further composed of an electroless gold plating film, which is also a preferred embodiment of the electroless palladium plating film.
本發明亦包含一種具有上述無電解鈀鍍敷被膜而成的電子機器構成零件。 [發明的效果]The present invention also includes an electronic device component having the electroless palladium plating film. [Effects of the invention]
藉由使用本發明的無電解Pd鍍敷液，所得到的Pd鍍敷被膜係可構成即使是在迴焊處理等的高溫熱歷程之後亦具有優異的導線接合性的鍍敷被膜。By using the electroless Pd plating solution of the present invention, the resulting Pd plating film can constitute a plating film having excellent wire bonding properties even after a high-temperature thermal history such as reflow processing.
[實施發明之最佳形態][The best way to implement the invention]
於Pd鍍敷被膜上形成Au鍍敷被膜而成的積層鍍敷被膜(以下有稱為「Pd/Au積層鍍敷被膜」之情形)，若被暴露於迴焊等的高溫熱歷程的話，之後的導線接合(wire bonding)的接續成功率會顯著地降低，本發明人們係對於該原因進行了深入之研究。其結果係認為，當被暴露於高溫熱歷程時，Pd會於Au鍍敷被膜表面進行擴散，而在Au鍍敷被膜表面形成Pd-Au固溶體，起因於該固溶體而使得導線接合的接續成功率降低。作為如此般的問題之解決方案之一係認為是可形成較厚的Au鍍敷被膜，但會使成本大幅上昇。If a laminated plating film in which an Au plating film is formed on a Pd plating film (hereinafter referred to as "Pd/Au laminated plating film") is exposed to a high-temperature thermal process such as reflow, The success rate of subsequent wire bonding will be significantly reduced, and the inventors have conducted in-depth research on this reason. As a result, it is believed that when exposed to a high-temperature thermal process, Pd diffuses on the surface of the Au plating film and forms a Pd-Au solid solution on the surface of the Au plating film. This solid solution causes the wire to The splicing success rate decreases. One solution to such a problem is to form a thicker Au plating film, but this will significantly increase the cost.
本發明人們更進一步重複研究之結果發現，只要形成含有P及B之雙方的Pd鍍敷被膜(以下有稱為「P-B-Pd三元系合金被膜」之情形)來作為Au鍍敷被膜的底層的話，則可改善高溫熱歷程後的導線接合性。亦即，使Pd鍍敷被膜中含有P與B之雙方時，即使是受到高溫熱歷程，亦可抑制在Au鍍敷被膜表面的Pd-Au固溶體的形成，其結果得知，可得到和以往的Au鍍敷被膜為同等程度，或是即使該厚度為較薄之情形亦比以往為具有更優異的導線接合性。As a result of further repeated studies, the present inventors found that it is only necessary to form a Pd plating film containing both P and B (hereinafter referred to as a "P-B-Pd ternary alloy film") as the base layer of the Au plating film. If so, the wire bonding properties after high-temperature thermal history can be improved. That is, when the Pd plating film contains both P and B, even if it is subjected to a high-temperature thermal history, the formation of Pd-Au solid solution on the surface of the Au plating film can be suppressed. As a result, it was found that The result is a wire bonding property that is equivalent to that of conventional Au plating films, or even if the thickness is thinner than that of conventional Au plating films.
能得到如此般效果的P-B-Pd三元系合金被膜，可藉由使用本發明的無電解Pd鍍敷液而容易形成。具體而言，本發明的無電解Pd鍍敷液為含有鈀化合物、選自由次亞磷酸化合物及亞磷酸化合物所成之群中之至少1種、選自由胺硼烷化合物及氫硼化合物所成之群中之至少1種與錯合劑而成的無電解Pd鍍敷液。A P-B-Pd ternary alloy film that can obtain such effects can be easily formed by using the electroless Pd plating solution of the present invention. Specifically, the electroless Pd plating solution of the present invention contains a palladium compound, at least one selected from the group consisting of hypophosphite compounds and phosphorous acid compounds, and a compound selected from the group consisting of an amine borane compound and a hydrogen boron compound. An electroless Pd plating solution composed of at least one of the group and a complex agent.
尚，使用於無電解Pd鍍敷液的還原劑係已知有複數種，本發明的鍍敷液中所使用的次亞磷酸化合物、亞磷酸化合物、胺硼烷化合物及氫硼化合物亦為其一部分。然而，以往以來若併用還原能力為不同的複數種的還原劑時，鍍敷液的穩定性會變差、產生異常析出等而鍍敷被膜特性會惡化，因而並未將還原劑予以併用。特別是次亞磷酸化合物或亞磷酸化合物，以單獨時即具有充分的還原能力，故完全未有與其他的還原劑併用之必要性。但明確得知，抑制因熱歷程所造成的Pd的對於Au鍍敷被膜的固溶之效果，以單獨添加還原劑或併用上述以外的還原劑時，將無法得到該效果，僅在本發明的上述特定的組合中，才不會產生上述問題，並能以實用等級來形成Pd鍍敷被膜，之同時，如此般的抑制固溶之效果，係僅能以上述之組合而得到的特有效果。Furthermore, a plurality of reducing agents used in electroless Pd plating solutions are known, and hypophosphite compounds, phosphorous acid compounds, amine borane compounds and hydrogen boron compounds used in the plating solution of the present invention are also among them. part. However, conventionally, when a plurality of reducing agents with different reducing abilities were used together, the stability of the plating solution would deteriorate, abnormal precipitation would occur, and the properties of the plating film would deteriorate. Therefore, reducing agents were not used together. In particular, hypophosphite compounds or phosphorous acid compounds have sufficient reducing power when used alone, so there is no need to use them in combination with other reducing agents. However, it is clearly known that the effect of suppressing the solid solution of Pd in the Au plating film due to thermal history cannot be obtained by adding a reducing agent alone or using a reducing agent other than the above in combination. Therefore, only in the present invention The above-mentioned specific combination does not cause the above-mentioned problems and can form a Pd plating film at a practical level. At the same time, such an effect of suppressing solid solution is a unique effect that can only be obtained by the above-mentioned combination.
鈀化合物 鈀化合物為用來得到鈀鍍敷的鈀離子的供給源。作為鈀化合物，只要是水溶性即可，可使用例如氯化鈀、硫酸鈀、乙酸鈀等的無機水溶性鈀鹽；四胺鈀鹽酸鹽、四胺鈀硫酸鹽、四胺鈀乙酸鹽、四胺鈀硝酸鹽、二氯二乙二胺鈀等的有機水溶性鈀鹽等。該等的鈀化合物可單獨或混合2種以上來使用。無電解Pd鍍敷液中的Pd離子濃度為未限定，但Pd離子濃度過低的話，鍍敷被膜的析出速度會有顯著降低之情形。另一方面，Pd離子濃度過高的話，因為異常析出等而被膜物性會有降低之虞。因此，鍍敷液中的鈀化合物的含有量，以作為Pd離子濃度而言較佳為0.01g/L以上，又較佳為0.1g/L以上，更佳為0.3g/L以上，又更佳為0.5g/L以上；且較佳為10g/L以下，又較佳為5g/L以下，更佳為3g/L以下。尚，可藉由使用原子吸收光譜光度計的原子吸收光譜分析(Atomic Absorption Spectrometry，AAS)來測定Pd離子。Palladium compound The palladium compound is a supply source of palladium ions used to obtain palladium plating. As the palladium compound, any water-soluble palladium compound may be used. For example, inorganic water-soluble palladium salts such as palladium chloride, palladium sulfate, and palladium acetate; tetraaminepalladium hydrochloride, tetraaminepalladium sulfate, tetraaminepalladium acetate, Organic water-soluble palladium salts such as tetraamine palladium nitrate and dichlorodiethylenediamine palladium. These palladium compounds can be used individually or in mixture of 2 or more types. The Pd ion concentration in the electroless Pd plating solution is not limited, but if the Pd ion concentration is too low, the deposition rate of the plating film will be significantly reduced. On the other hand, if the Pd ion concentration is too high, the physical properties of the film may be reduced due to abnormal precipitation, etc. Therefore, the content of the palladium compound in the plating solution is preferably 0.01g/L or more as a Pd ion concentration, more preferably 0.1g/L or more, more preferably 0.3g/L or more, and more preferably 0.3g/L or more. It is preferably 0.5g/L or more; more preferably it is 10g/L or less, further preferably 5g/L or less, and more preferably 3g/L or less. However, Pd ions can be measured by atomic absorption spectrometry (AAS) using an atomic absorption spectrophotometer.
本發明的無電解Pd鍍敷液，為了使發揮抑制Pd的固溶之效果，必須併用(1)選自由次亞磷酸化合物及亞磷酸化合物所成之群中之至少1種(以下有稱為「磷酸化合物」之情形)、與(2)選自由胺硼烷化合物及氫硼化合物所成之群中之至少1種(以下有稱為「硼化合物」之情形)。In order to exert the effect of inhibiting the solid solution of Pd, the electroless Pd plating solution of the present invention must contain (1) at least one selected from the group consisting of hypophosphite compounds and phosphorous acid compounds (hereinafter referred to as In the case of "phosphoric acid compounds"), and (2) at least one selected from the group consisting of amine borane compounds and hydrogen boron compounds (hereinafter referred to as "boron compounds").
(1)選自由次亞磷酸化合物及亞磷酸化合物所成之群中之至少1種 該等為對於Pd鍍敷被膜的P供給源，之同時，在無電解Pd鍍敷液中係作用作為使Pd析出的還原劑。作為次亞磷酸化合物，可示例次亞磷酸、及次亞磷酸鈉等的次亞磷酸鹽，作為亞磷酸化合物，可示例亞磷酸、及亞磷酸鈉等的亞磷酸鹽。次亞磷酸化合物及亞磷酸化合物可單獨或組合來使用。若無電解Pd鍍敷液中的次亞磷酸化合物、及/或亞磷酸化合物的含有量過少的話，鍍敷處理時的析出速度會降低，之同時，將無法充分地得到抑制因高溫熱歷程所造成的Pd的對於Au鍍敷被膜的固溶之效果，導線接合性會有惡化之情形。若無電解Pd鍍敷液中的次亞磷酸化合物及亞磷酸化合物的含有量越多時，會越提升上述抑制固溶之效果，但無電解Pd鍍敷液的穩定性會有降低之情形。無電解Pd鍍敷液中的次亞磷酸化合物及亞磷酸化合物的含有量(若以單獨來含有時，則為單獨的量；若含有2種以上時，則為合計量)較佳為0.1g/L以上，又較佳為0.5g/L以上，更佳為1g/L以上，又更佳為2g/L以上；且較佳為100g/L以下，又較佳為50g/L以下，更佳為20g/L以下，又更佳為15g/L以下。(1) At least one selected from the group consisting of hypophosphite compounds and phosphorous acid compounds These are P supply sources to the Pd plating film and act as reducing agents for precipitating Pd in the electroless Pd plating solution. Examples of the hypophosphite compound include hypophosphites such as hypophosphite and sodium hypophosphite. Examples of the hypophosphite compound include phosphorous acid and phosphites such as sodium phosphite. Hypophosphite compounds and phosphorous acid compounds can be used alone or in combination. If the content of the hypophosphite compound and/or the phosphorous acid compound in the electroless Pd plating solution is too small, the precipitation rate during the plating process will be reduced, and at the same time, the high-temperature thermal history will not be sufficiently suppressed. The resulting solid solution effect of Pd on the Au plating film may deteriorate the wire bonding properties. If the content of the hypophosphite compound and the phosphorous acid compound in the electroless Pd plating solution increases, the above-mentioned effect of inhibiting solid solution will be enhanced, but the stability of the electroless Pd plating solution will be reduced. The content of the hypophosphite compound and the phosphorous acid compound in the electroless Pd plating solution (when contained individually, it is the individual amount; when two or more types are contained, it is the total amount) is preferably 0.1 g. /L or more, preferably 0.5g/L or more, more preferably 1g/L or more, still more preferably 2g/L or more; and preferably 100g/L or less, more preferably 50g/L or less, more preferably Preferably, it is 20g/L or less, and more preferably, it is 15g/L or less.
(2)選自由胺硼烷化合物及氫硼化合物所成之群中之至少1種 該等為對於Pd鍍敷被膜的硼供給源，之同時，在無電解Pd鍍敷液中係作用作為使鈀析出的還原劑。作為胺硼烷化合物，可示例二甲基胺硼烷(DMAB)、及三甲基胺硼烷(TMAB)；作為氫硼化合物，可示例硼氫化鈉(SBH)、及硼氫化鉀(KBH)等的硼氫化鹼金屬鹽。本發明中係以使用選自由二甲基胺硼烷、三甲基胺硼烷、硼氫化鈉、及硼氫化鉀所成之群中之至少1種為較佳。若無電解Pd鍍敷液中的硼化合物的含有量過少的話，鍍敷處理時的析出速度會降低，之同時，將無法充分地得到抑制因高溫熱歷程所造成的Pd的對於Au鍍敷被膜的固溶之效果，導線接合性會有惡化之情形。無電解Pd鍍敷液中的硼化合物含有量越多時，會越提升上述抑制固溶之效果，但無電解Pd鍍敷液的穩定性會有降低之情形。無電解Pd鍍敷液中的硼化合物的含有量(若以單獨來含有時，則為單獨的量；若含有2種以上時，則為合計量)較佳為0.01g/L以上，又較佳為0.1g/L以上，更佳為0.5g/L以上，又更佳為1g/L以上；且較佳為100g/L以下，又較佳為50g/L以下，更佳為30g/L以下，又更佳為20g/L。(2) At least one selected from the group consisting of amine borane compounds and hydrogen boron compounds These are boron supply sources for the Pd plating film and act as reducing agents for precipitating palladium in the electroless Pd plating solution. Examples of the amine borane compound include dimethylamine borane (DMAB) and trimethylamine borane (TMAB); examples of the borohydride compound include sodium borohydride (SBH) and potassium borohydride (KBH). Alkali metal borohydride salts. In the present invention, it is preferred to use at least one selected from the group consisting of dimethylamine borane, trimethylamine borane, sodium borohydride, and potassium borohydride. If the content of the boron compound in the electroless Pd plating solution is too small, the precipitation rate during the plating process will be reduced, and at the same time, the effect of Pd on Au plating due to high-temperature thermal history will not be sufficiently suppressed. Due to the solid solution effect of the film, the wire bonding properties may be deteriorated. The greater the boron compound content in the electroless Pd plating solution, the greater the effect of suppressing solid solution, but the stability of the electroless Pd plating solution may decrease. The content of the boron compound in the electroless Pd plating solution (if it is contained individually, it is the individual amount; if it contains two or more types, it is the total amount) is preferably 0.01g/L or more, and is preferably Preferably it is 0.1g/L or more, more preferably 0.5g/L or more, and more preferably 1g/L or more; and more preferably 100g/L or less, more preferably 50g/L or less, more preferably 30g/L below, and preferably 20g/L.
錯合劑 錯合劑係主要具有使無電解Pd鍍敷液中的Pd的溶解性呈穩定化之作用。作為錯合劑，可使用各種周知的錯合劑，較佳為選自由氨及胺化合物所成之群中之至少1種，又較佳為胺化合物。作為胺化合物，可舉出甲基胺、二甲基胺、三甲基胺、苄基胺、亞甲基二胺、乙二胺、乙二胺衍生物、四亞甲基二胺、二伸乙三胺、乙二胺四乙酸(Ethylene Diamine Tetraacetic Acid：EDTA)、或其鹼金屬鹽、EDTA衍生物、甘胺酸等。錯合劑可單獨、或合併2種以上來使用。無電解Pd鍍敷液中的錯合劑的含有量(若以單獨來含有時，則為單獨的量；若含有2種以上時，則為合計量)，以能獲得上述作用之方式來適當進行調整即可，較佳為0.5g/L以上，又較佳為1g/L以上，更佳為3g/L以上，又更佳為5g/L以上；且較佳為50g/L以下，又較佳為30g/L以下。Mixture The complexing agent mainly has the function of stabilizing the solubility of Pd in the electroless Pd plating solution. As the complexing agent, various well-known complexing agents can be used, and at least one selected from the group consisting of ammonia and amine compounds is preferred, and an amine compound is more preferred. Examples of the amine compound include methylamine, dimethylamine, trimethylamine, benzylamine, methylenediamine, ethylenediamine, ethylenediamine derivatives, tetramethylenediamine, and diethylenediamine. Ethylene Diamine Tetraacetic Acid (EDTA), or its alkali metal salt, EDTA derivatives, glycine, etc. The complex agent can be used alone or in combination of two or more types. The content of the complexing agent in the electroless Pd plating solution (if it is contained individually, it is the individual amount; if it contains two or more types, it is the total amount), is appropriately determined in such a manner that the above effects can be obtained. Just adjust it, preferably 0.5g/L or more, more preferably 1g/L or more, more preferably 3g/L or more, more preferably 5g/L or more; and preferably 50g/L or less, and more preferably 50g/L or less. Preferably it is below 30g/L.
本發明的無電解Pd鍍敷液，若含有上述成分組成時，則可得到上述效果，因而能僅以上述成分組成來構成本發明的無電解Pd鍍敷液，但因應所需亦可含有pH調整劑、穩定化劑等的各種添加劑。If the electroless Pd plating solution of the present invention contains the above-mentioned component composition, the above-mentioned effects can be obtained. Therefore, the electroless Pd plating solution of the present invention can be constituted only with the above-mentioned component composition. However, it may also contain pH as needed. Various additives such as regulators and stabilizers.
pH調整劑 本發明的無電解Pd鍍敷液，若pH過低的話，Pd的析出速度會容易降低，另一方面，若pH過高的話，無電解Pd鍍敷液的穩定性會有降低之情形。較佳為pH4~10，又較佳為pH6~8。無電解Pd鍍敷液的pH，可添加周知的pH調整劑來進行調整。作為pH調整劑，可舉例如鹽酸、硫酸、硝酸、檸檬酸、丙二酸、蘋果酸、酒石酸、磷酸等的酸、氫氧化鈉、氫氧化鉀、氨水等的鹼。該等能以1種或合併2種以上來使用。pH adjuster If the pH of the electroless Pd plating solution of the present invention is too low, the precipitation rate of Pd will tend to decrease. On the other hand, if the pH is too high, the stability of the electroless Pd plating solution will decrease. Preferably, pH is 4~10, and more preferably, pH is 6~8. The pH of the electroless Pd plating solution can be adjusted by adding a known pH adjuster. Examples of the pH adjuster include acids such as hydrochloric acid, sulfuric acid, nitric acid, citric acid, malonic acid, malic acid, tartaric acid, and phosphoric acid, and bases such as sodium hydroxide, potassium hydroxide, and ammonia water. These can be used as one type or in combination of two or more types.
穩定化劑 穩定化劑為依據鍍敷穩定性、鍍敷後的外觀的提升、鍍敷被膜形成的速度調整等的目的，因應所需所添加的。本發明的無電解Pd鍍敷液，可進一步含有周知的含硫磺化合物。作為含硫磺化合物，較佳為例如選自硫醚化合物、硫氰酸化合物、硫代羰基化合物、硫醇化合物、硫代硫酸及硫代硫酸鹽之1種或2種以上。具體而言可舉出甲硫胺酸、二甲基亞碸、硫代二乙醇酸、苯并噻唑等的硫醚化合物；硫氰酸、硫氰酸鉀、硫氰酸鈉、硫氰酸銨等的硫氰酸化合物；硫代脲或其衍生物等的硫代羰基化合物；半胱胺酸、硫代乳酸、硫代乙醇酸、巰基乙醇、丁硫醇等的硫醇化合物；硫代硫酸鈉等的硫代硫酸鹽。該等的含硫磺化合物可單獨、或亦可混合二種以上來使用。無電解Pd鍍敷液中的穩定化劑的含有量(若以單獨來含有時，則為單獨的量；若含有2種以上時，則為合計量)，以能獲得鍍敷穩定性等的效果之方式來適當進行調整即可，較佳為0.1mg/L以上，又較佳為0.5mg/L以上；較佳為500mg/L以下，又較佳為100mg/L以下。stabilizer Stabilizers are added as needed for the purposes of plating stability, improving the appearance after plating, adjusting the speed of plating film formation, etc. The electroless Pd plating solution of the present invention may further contain a known sulfur-containing compound. As the sulfur-containing compound, for example, one or two or more types selected from the group consisting of thioether compounds, thiocyanate compounds, thiocarbonyl compounds, thiol compounds, thiosulfuric acid and thiosulfate salts are preferred. Specific examples include thioether compounds such as methionine, dimethylsyanine, thiodiglycolic acid, and benzothiazole; thiocyanic acid, potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate. Thiocyanic acid compounds such as thiourea or its derivatives; thiocarbonyl compounds such as thiourea or its derivatives; thiol compounds such as cysteine, thiolactic acid, thioglycolic acid, mercaptoethanol, butanethiol, etc.; thiosulfuric acid Sodium thiosulfate etc. These sulfur-containing compounds may be used individually or in mixture of two or more types. The content of the stabilizer in the electroless Pd plating solution (if it is contained alone, it is the individual amount; if it contains two or more kinds, it is the total amount), so that plating stability, etc. can be obtained It just needs to be adjusted appropriately according to the effect, preferably 0.1 mg/L or more, more preferably 0.5 mg/L or more; preferably 500 mg/L or less, and more preferably 100 mg/L or less.
尚，本發明的無電解Pd鍍敷液中不含有界面活性劑。若本發明的無電解Pd鍍敷液中添加界面活性劑的話，所得到的Pd鍍敷被膜表面會成為吸附界面活性劑之狀態，而Au鍍敷被膜的成膜性會劣化。其結果，導線接合性亦會惡化。所謂的界面活性劑為各種周知的非離子性、陽離子性、陰離子性、及兩性界面活性劑。Furthermore, the electroless Pd plating solution of the present invention does not contain surfactant. If a surfactant is added to the electroless Pd plating solution of the present invention, the surface of the resulting Pd plating film will be in a state where the surfactant is adsorbed, and the film-forming properties of the Au plating film will be deteriorated. As a result, the wire bondability also deteriorates. The so-called surfactants are various well-known nonionic, cationic, anionic, and amphoteric surfactants.
本發明係包含使用上述無電解Pd鍍敷液而成的含有P及B的Pd鍍敷被膜。抑制Pd的固溶之效果，以Pd鍍敷被膜中含有P及B之雙方時即可得到該效果，故各含有量為未限定，但Pd鍍敷被膜中所含有的P或B的含有量若增加的話，可得到更優異的抑制Pd的固溶之效果。Pd鍍敷被膜中的P含有量，較佳為0.1質量%以上，又較佳為0.3質量%以上；較佳為10質量%以下，又較佳為5質量%以下。又，Pd鍍敷被膜中的B含有量，較佳為0.1質量%以上，又較佳為0.5質量%以上；較佳為15質量%以下，又較佳為10質量%以下。又，藉由適當地控制P與B的比率，可得到更優異的抑制Pd的固溶之效果。無電解Pd鍍敷被膜中的P與B的含有量的質量比率(P:B)，較佳為10:1~1:10，又較佳為5:1~1:5。本發明的Pd鍍敷被膜只要是含有P、B，亦可進一步含有來自於上述各種添加劑的成分。其餘部分為Pd、及不可避免的雜質。The present invention includes a Pd plating film containing P and B using the electroless Pd plating solution described above. The effect of suppressing the solid solution of Pd can be obtained when the Pd plating film contains both P and B, so the content of each is not limited, but the content of P or B contained in the Pd plating film If it is increased, a more excellent effect of inhibiting the solid solution of Pd can be obtained. The P content in the Pd plating film is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, and more preferably 5% by mass or less. In addition, the B content in the Pd plating film is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and is preferably 15 mass% or less, further preferably 10 mass% or less. In addition, by appropriately controlling the ratio of P and B, a more excellent effect of suppressing the solid solution of Pd can be obtained. The mass ratio (P:B) of the content of P and B in the electroless Pd plating film is preferably 10:1 to 1:10, and more preferably 5:1 to 1:5. As long as the Pd plating film of the present invention contains P and B, it may further contain components derived from the various additives mentioned above. The remainder is Pd and inevitable impurities.
本發明的無電解Pd鍍敷液亦較佳適合於Pd/Au積層鍍敷被膜用途，該Pd/Au積層鍍敷被膜，係對於電子零件的接合用鍍敷等中所使用的Pd鍍敷被膜積層Au鍍敷被膜而成。因此，將具有本發明的Pd鍍敷被膜與Au鍍敷被膜的積層鍍敷被膜亦設定為較佳的實施樣態。本發明的Pd鍍敷被膜，至少在積層Au鍍敷被膜而成的Pd/Au積層鍍敷被膜中係可確認抑制Pd的固溶之效果。因此，形成Pd鍍敷被膜的基底為無限定，可舉出Al或Al基合金、Cu或Cu基合金等各種周知的基材、或以Fe、Co、Ni、Cu、Zn、Ag、Au、Pt等、及該等的合金等的對於Pd鍍敷被膜的還原析出具有觸媒性的金屬來被覆基材而成的鍍敷被膜。又，即便是不具有觸媒性的金屬，亦可藉由各種的方法而作為被鍍敷物使用。The electroless Pd plating solution of the present invention is also preferably suitable for use as a Pd/Au laminated plating film, which is a Pd plating film used in plating for bonding electronic parts, etc. It is made of laminated Au plating film. Therefore, a laminated plating film having the Pd plating film and the Au plating film of the present invention is also a preferred embodiment. The Pd plating film of the present invention has an effect of suppressing the solid solution of Pd, at least in a Pd/Au laminated plating film in which an Au plating film is laminated. Therefore, the substrate on which the Pd plating film is formed is not limited, and may include various well-known substrates such as Al or Al-based alloys, Cu or Cu-based alloys, or Fe, Co, Ni, Cu, Zn, Ag, Au, A plating film formed by coating a base material with a metal that catalytically precipitates the reduction of Pd plating film such as Pt and its alloys. In addition, even metals that do not have catalytic properties can be used as the object to be plated by various methods.
又，作為較佳的其他的實施樣態，本發明的無電解Pd鍍敷液為可適用於ENEPIG製程。ENEPIG製程係例如，在構成電極的Al或Al基合金、Cu或Cu基合金上形成Ni鍍敷被膜，接下來為形成Pd鍍敷被膜，接下來在其上方形成Au鍍敷被膜，藉此可得到包含本發明的Pd鍍敷被膜的無電解Ni/Pd/Au鍍敷被膜。尚，各鍍敷被膜之形成，採用一般所進行之方法即可。以下為依據ENEPIG製程來對於具有本發明的Pd鍍敷被膜的無電解Ni/Pd/Au鍍敷被膜的製造方法進行說明，但本發明的Pd鍍敷被膜的形成條件並不被限定於此，可依據周知技術來進行適當變更。In addition, as another preferred embodiment, the electroless Pd plating solution of the present invention is applicable to the ENEPIG process. The ENEPIG process, for example, forms a Ni plating film on Al or Al-based alloy, Cu or Cu-based alloy constituting the electrode, then forms a Pd plating film, and then forms an Au plating film on top of it. An electroless Ni/Pd/Au plating film including the Pd plating film of the present invention was obtained. However, the formation of each plating film can be carried out by generally used methods. The following is a description of a method for manufacturing an electroless Ni/Pd/Au plating film having a Pd plating film of the present invention based on the ENEPIG process. However, the formation conditions of the Pd plating film of the present invention are not limited thereto. Appropriate changes may be made based on well-known technology.
使用無電解Ni鍍敷液來進行無電解Ni鍍敷時的鍍敷條件及鍍敷裝置並未特別限定，可適當地選擇各種的周知的方法。例如，使被鍍敷物接觸於溫度50~95℃的無電解Ni鍍敷液15~60分左右即可。因應所要求特性來適當設定Ni鍍敷被膜的膜厚即可，通常為3~7μm左右。又，無電解Ni鍍敷液中可使用Ni-P合金、Ni-B合金等各種的周知的組成。The plating conditions and plating equipment when performing electroless Ni plating using an electroless Ni plating solution are not particularly limited, and various known methods can be appropriately selected. For example, the object to be plated may be exposed to an electroless Ni plating solution with a temperature of 50 to 95°C for about 15 to 60 minutes. The film thickness of the Ni plating film can be appropriately set according to the required characteristics, usually about 3 to 7 μm. In addition, various well-known compositions such as Ni-P alloy and Ni-B alloy can be used in the electroless Ni plating solution.
使用本發明的無電解Pd鍍敷液來進行無電解Pd鍍敷時的鍍敷條件及鍍敷裝置並未特別限定，可適當地選擇各種的周知的方法。例如，使形成有Ni鍍敷被膜的被鍍敷物接觸於溫度50~95℃的無電解Pd鍍敷液15~60分左右即可。因應所要求特性來適當設定Pd鍍敷被膜的膜厚即可，通常為0.001~0.5μm左右。The plating conditions and plating equipment when performing electroless Pd plating using the electroless Pd plating solution of the present invention are not particularly limited, and various known methods can be appropriately selected. For example, the object to be plated on which the Ni plating film is formed is contacted with an electroless Pd plating solution having a temperature of 50 to 95°C for about 15 to 60 minutes. The film thickness of the Pd plating film can be appropriately set according to the required characteristics, usually around 0.001~0.5μm.
使用無電解金鍍敷液來進行無電解金鍍敷時的鍍敷條件及鍍敷裝置並未特別限定，可適當地選擇各種的周知的方法。例如，使形成有Pd鍍敷被膜的被鍍敷物接觸於溫度40~90℃的無電解金鍍敷液3~20分左右即可。因應所要求特性來適當設定金鍍敷被膜的膜厚即可，通常為0.01~2μm左右。The plating conditions and plating equipment when performing electroless gold plating using an electroless gold plating solution are not particularly limited, and various known methods can be appropriately selected. For example, the object to be plated with a Pd plating film is brought into contact with an electroless gold plating solution having a temperature of 40 to 90° C. for about 3 to 20 minutes. The film thickness of the gold plating film can be appropriately set according to the required characteristics, usually around 0.01~2μm.
只要使用本發明的Pd鍍敷被膜，由於可抑制在迴焊處理等的鍍敷被膜形成後的安裝步驟的熱歷程所造成的來自Pd鍍敷被膜的鈀的對於Au鍍敷被膜之擴散、固溶，故可實現即使是熱歷程後亦為優異的導線接合性。熱歷程的溫度為在安裝步驟中所假想之溫度，未特別限定。只要使用本發明的Pd鍍敷被膜，即使是例如50℃以上(又較佳為100℃以上)的高溫熱歷程後，亦可實現優異的導線接合性。By using the Pd plating film of the present invention, diffusion and fixation of palladium from the Pd plating film to the Au plating film due to the thermal history of the mounting step after the plating film is formed such as reflow processing can be suppressed. Because it dissolves, excellent wire bonding properties can be achieved even after thermal history. The temperature of the thermal history is the temperature assumed in the installation step and is not particularly limited. By using the Pd plating film of the present invention, excellent wire bonding properties can be achieved even after a high-temperature thermal history of, for example, 50° C. or higher (preferably 100° C. or higher).
電子機器構成零件 本發明亦包含具有上述鍍敷被膜而成的電子機器構成零件。作為電子機器構成零件，可舉例如構成晶片零件、水晶振動器、凸塊、連接器、引線框架、環箍材料、半導體封裝體、印刷基板等的電子機器的零件。特別是適合使用於，以對於晶圓上的Al電極或Cu電極進行焊錫接合及導線接合(W/B)之接合目的之UBM(Under Barrier Metal)形成技術。藉由將Au鍍敷被膜積層於使用本發明的無電解Pd鍍敷液所形成的Pd鍍敷被膜上，即使是熱歷程後亦可實現優異的導線接合性。Electronic machine components The present invention also includes electronic equipment components having the above-mentioned plating film. Examples of components constituting electronic equipment include components constituting electronic equipment such as wafer parts, crystal vibrators, bumps, connectors, lead frames, hoop materials, semiconductor packages, and printed circuit boards. It is particularly suitable for use in UBM (Under Barrier Metal) formation technology for the purpose of solder bonding and wire bonding (W/B) of Al electrodes or Cu electrodes on wafers. By laminating the Au plating film on the Pd plating film formed using the electroless Pd plating solution of the present invention, excellent wire bonding properties can be achieved even after thermal history.
本專利申請案係基於2017年10月6日所提出的日本國特願第2017-195651號來主張優先權之權益。將2017年10月6日所提出的日本國特願第2017-195651號申請案的說明書全内容予以參考並援用至本案。 [實施例]This patent application claims priority based on Japanese Special Application No. 2017-195651 filed on October 6, 2017. The entire description of Japanese Special Application No. 2017-195651 filed on October 6, 2017 is hereby referred to and incorporated into this case. [Example]
以下為舉出實施例來更具體地說明本發明，但本發明當然不因下述實施例而受限，在能夠適合於前、後文要旨之範圍內，自可適當加以變更並實施，而該等均包含於本發明的技術範圍內。The following examples are given to illustrate the present invention in more detail. However, the present invention is of course not limited by the following examples, and can be appropriately modified and implemented within the scope of the foregoing and following gist. These are all included in the technical scope of the present invention.
對於BGA基板(Ball Grid Array:上村工業公司製、5cm×5cm)依序進行表1所示的前處理、鍍敷處理，來製造從基板側起依序為形成Ni鍍敷被膜、Pd鍍敷被膜、Au鍍敷被膜的試片1~20。調查所得到的試片的導線接合性。The BGA substrate (Ball Grid Array: manufactured by Uemura Industrial Co., Ltd., 5cm×5cm) is manufactured by sequentially performing the preprocessing and plating treatments shown in Table 1 to form a Ni plating film and Pd plating in order from the substrate side. Samples 1 to 20 of coating and Au plating coating. The wire bondability of the obtained test pieces was investigated.
導線接合性 以試驗裝置(TPT公司製Semiautomatic wire bonder HB16)來進行導線接合，藉由Dage公司製接合測試機(bond tester)SERIES4000並依據下述測定條件，來對於每1條件評估20點。尚，測定為在熱處理前、及熱處理後(以175℃保持16小時)來進行。作為導線接合性評估，若熱處理後的導線接合平均強度為9.0g以上時，則評估為「優」，若為8.5g以上、未滿9.0g時，則評估為「良」，若為7.5g以上、未滿8.5g時，則評估為「可」，若為未滿7.5g時，則評估為「不良」。Wire bondability Wire bonding was performed using a test device (Semiautomatic wire bonder HB16 manufactured by TPT Corporation), and 20 points were evaluated for each condition using a bond tester (bond tester) SERIES4000 manufactured by Dage Corporation based on the following measurement conditions. Note that the measurement was performed before the heat treatment and after the heat treatment (maintained at 175° C. for 16 hours). As for the evaluation of wire bondability, if the average wire bonding strength after heat treatment is 9.0g or more, it is evaluated as "excellent"; if it is 8.5g or more and less than 9.0g, it is evaluated as "good"; if it is 7.5g, it is evaluated as "good" If it is above and less than 8.5g, it will be evaluated as "acceptable", and if it is less than 7.5g, it will be evaluated as "poor".
[測定條件] 銲針：B1014-51-18-12(PECO公司製) 導線：1mil-Au導線(SPM公司製) 平臺溫度：150℃ 超音波(mW)：250(1st)、250(2nd) 接合時間(毫秒)：200(1st)、50(2nd) 拉力(gf)：25(1st)、50(2nd) 步驟(第1位置至第2位置之長度)：0.7mm 測定方式：導線拉力測試 裝置：萬能型接合測試機#4000(Nordson Advanced Technology公司製) 試驗速度：170μm/秒[Measurement conditions] Soldering pin: B1014-51-18-12 (manufactured by PECO Corporation) Lead wire: 1mil-Au lead wire (manufactured by SPM Corporation) Platform temperature: 150℃ Ultrasonic (mW): 250(1st), 250(2nd) Engagement time (milliseconds): 200 (1st), 50 (2nd) Pulling force (gf): 25(1st), 50(2nd) Step (length from 1st position to 2nd position): 0.7mm Measurement method: Wire tension test Device: Universal bonding tester #4000 (manufactured by Nordson Advanced Technology Co., Ltd.) Test speed: 170μm/second
如表2所示般，使用本發明所界定的包含[錯合劑]、[次亞磷酸化合物、及/或亞磷酸化合物]、與[胺硼烷化合物、及/或氫硼化合物]的無電解Pd鍍敷液而成的試片No.1~9，該等的熱處理後的導線接合性均為「良」之評估以上。As shown in Table 2, an electroless compound containing [complexing agent], [hypophosphite compound, and/or phosphorous acid compound], and [amine borane compound, and/or hydrogen boron compound] as defined in the present invention is used. For test pieces No. 1 to 9 made of Pd plating solution, the wire bonding properties after heat treatment were all rated as "good" or above.
另一方面，使用未滿足本發明所界定的Pd鍍敷液而成的No.10~18，該等的熱處理後的導線接合性均為「不良」之評估。尚，由於No.19與No.20為含有界面活性劑，故熱處理後的導線接合性均為「不良」之評估。On the other hand, for Nos. 10 to 18 using a Pd plating solution that did not meet the definition of the present invention, the wire bonding properties after heat treatment were all evaluated as "poor". However, since No. 19 and No. 20 contain surfactants, the wire bonding properties after heat treatment were both evaluated as "poor".
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| JP2017195651A JP7149061B2 (en) | 2017-10-06 | 2017-10-06 | Electroless palladium plating solution |
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| EP (1) | EP3693495A4 (en) |
| JP (1) | JP7149061B2 (en) |
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| JP2007009305A (en) * | 2005-07-04 | 2007-01-18 | Japan Pure Chemical Co Ltd | Electroless palladium plating liquid, and three layer-plated film terminal formed using the same |
| JP2011225927A (en) * | 2010-04-19 | 2011-11-10 | Okuno Chemical Industries Co Ltd | Activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating |
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| JP2000256866A (en) * | 1999-03-10 | 2000-09-19 | Hideo Honma | Electroless nickel plating bath |
| CN101228293B (en) | 2005-07-20 | 2010-12-08 | 日矿金属株式会社 | Plating solution for electroless palladium plating |
| JP4974332B2 (en) * | 2005-09-07 | 2012-07-11 | 一般財団法人電力中央研究所 | Nanostructure and manufacturing method thereof |
| JP4511623B1 (en) * | 2009-05-08 | 2010-07-28 | 小島化学薬品株式会社 | Electroless palladium plating solution |
| US20140072706A1 (en) * | 2012-09-11 | 2014-03-13 | Ernest Long | Direct Electroless Palladium Plating on Copper |
| TWI707061B (en) * | 2015-11-27 | 2020-10-11 | 德商德國艾托特克公司 | Plating bath composition and method for electroless plating of palladium |
| JP6635304B2 (en) | 2016-04-18 | 2020-01-22 | 株式会社オートネットワーク技術研究所 | Relay device and in-vehicle system |
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- 2018-10-03 US US16/753,417 patent/US20200248312A1/en not_active Abandoned
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|---|---|---|---|---|
| JP2007009305A (en) * | 2005-07-04 | 2007-01-18 | Japan Pure Chemical Co Ltd | Electroless palladium plating liquid, and three layer-plated film terminal formed using the same |
| JP2011225927A (en) * | 2010-04-19 | 2011-11-10 | Okuno Chemical Industries Co Ltd | Activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating |
| TW201319315A (en) * | 2011-10-12 | 2013-05-16 | Atotech Deutschland Gmbh | Electroless palladium plating bath composition |
| TW201317389A (en) * | 2011-10-24 | 2013-05-01 | Kojima Chemicals Co Ltd | Electroless palladium plating solution |
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| EP3693495A4 (en) | 2021-09-29 |
| JP2019070172A (en) | 2019-05-09 |
| EP3693495A1 (en) | 2020-08-12 |
| JP7149061B2 (en) | 2022-10-06 |
| US20200248312A1 (en) | 2020-08-06 |
| KR20200062265A (en) | 2020-06-03 |
| TW201925531A (en) | 2019-07-01 |
| WO2019069964A1 (en) | 2019-04-11 |
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