JP5567478B2 - 銅系金属上のパラジウムめっき皮膜の製造方法及び該製造方法により得られるパラジウムめっき皮膜 - Google Patents
銅系金属上のパラジウムめっき皮膜の製造方法及び該製造方法により得られるパラジウムめっき皮膜 Download PDFInfo
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- JP5567478B2 JP5567478B2 JP2010519714A JP2010519714A JP5567478B2 JP 5567478 B2 JP5567478 B2 JP 5567478B2 JP 2010519714 A JP2010519714 A JP 2010519714A JP 2010519714 A JP2010519714 A JP 2010519714A JP 5567478 B2 JP5567478 B2 JP 5567478B2
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- copper
- catalyst
- gold
- palladium
- based metal
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 212
- 229910052763 palladium Inorganic materials 0.000 title claims description 106
- 238000007747 plating Methods 0.000 title claims description 100
- 239000010949 copper Substances 0.000 title claims description 84
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 83
- 229910052802 copper Inorganic materials 0.000 title claims description 83
- 229910052751 metal Inorganic materials 0.000 title claims description 70
- 239000002184 metal Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007788 liquid Substances 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 51
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 51
- 229910052737 gold Inorganic materials 0.000 claims description 51
- 239000010931 gold Substances 0.000 claims description 51
- 230000009467 reduction Effects 0.000 claims description 22
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 20
- 150000002344 gold compounds Chemical class 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 18
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 17
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 16
- 238000011156 evaluation Methods 0.000 description 32
- 229910000679 solder Inorganic materials 0.000 description 31
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000758 substrate Substances 0.000 description 19
- 239000004020 conductor Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 150000002941 palladium compounds Chemical class 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 4
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical group N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003536 tetrazoles Chemical group 0.000 description 2
- DIWZKTYQKVKILN-VKHMYHEASA-N (2s)-2-(dicarboxymethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(C(O)=O)C(O)=O DIWZKTYQKVKILN-VKHMYHEASA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- AXINVSXSGNSVLV-UHFFFAOYSA-N 1h-pyrazol-4-amine Chemical compound NC=1C=NNC=1 AXINVSXSGNSVLV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical group N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 1
- MWBWWFOAEOYUST-UHFFFAOYSA-N 2-aminopurine Chemical compound NC1=NC=C2N=CNC2=N1 MWBWWFOAEOYUST-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 235000011054 acetic acid Nutrition 0.000 description 1
- CKJBFEQMHZICJP-UHFFFAOYSA-N acetic acid;1,3-diaminopropan-2-ol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCC(O)CN CKJBFEQMHZICJP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003282 alkyl amino group Chemical group 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ADPOBOOHCUVXGO-UHFFFAOYSA-H dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(3+) Chemical compound [Au+3].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ADPOBOOHCUVXGO-UHFFFAOYSA-H 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000004867 thiadiazoles Chemical group 0.000 description 1
- 238000011077 uniformity evaluation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Description
本発明における「水溶性の金化合物」は、触媒付与液中の濃度が好適になるように水に溶解する程度の水溶性を有する金化合物であれば特に限定はないが、具体的には、例えば、シアン化金塩、塩化金塩、亜硫酸金塩、チオ硫酸金塩等が挙げられる。好ましくは、金化合物の安定性及び薬品の入手の容易さ等の点でシアン化金塩であり、特に好ましくは、シアン化第1金塩又はシアン化第2金塩である。対カチオンは特に限定はないが、触媒付与液を調製する際に加えるものとしては、アルカリ金属塩が好ましく、なかでもカリウム塩が特に好ましい。
本発明における「窒素原子が2個以上の5員環構造を有するヘテロ環化合物」とは、炭素以外の元素を有する芳香族性をもつ環(以下、「ヘテロ環」と略記する)を有する化合物であって、5員環構造を有し、その5員環を形成している原子のうち2個以上が窒素原子である構造を持つ化合物をいう。すなわち、「窒素原子が2個以上の5員環構造を有するヘテロ環化合物」とは、「『窒素原子が2個以上の5員環構造を有する』ヘテロ環化合物」をいう。
本発明における「イミノ2酢酸構造を有するキレート剤」としては、銅系導体回路等を構成する銅系金属を触媒付与液中に溶解可能なイミノ2酢酸構造を有するものであることが好ましい。イミノ2酢酸構造を有するキレート剤を必須成分として含有させることによって、銅系金属の触媒付与液への均一な溶解を促進するとともに、銅系金属が再析出するのを防止することができるため、触媒核の付与を均一かつ確実に行なうことができ、また微細配線間の絶縁体への金属付着による微細配線のブリッジ発生を防止することができる。
<触媒付与液の調製>
表1に示す(a)水溶性の金化合物を、金属金換算で触媒付与液全体に対して質量で100ppm、表1に示す(b)窒素原子が2個以上の5員環構造を有するヘテロ環化合物を、触媒付与液全体に対して質量で500ppm、表1に示す(c)イミノ2酢酸構造を有するキレート剤を、触媒付与液全体に対して20g/L、となるように純水に溶解させた。次いでpH5.0になるように調整して各触媒付与液を調製した。なお、pH調整は、pHを上げる時は水酸化ナトリウム水溶液を、下げる時は塩酸を使用した。
比較例1として、市販のパラジウムを含有する「無電解還元ニッケルめっき用の触媒付与液(KAT−450、上村工業株式会社製)」を、通常の使用状態に調整したものを用いた。また、比較例2として、市販のパラジウムを含有する「無電解還元ニッケルめっき用の触媒付与液(ICPアクセラ、奥野製薬株式会社製)」を、通常の使用状態に調整したものを用いた。
表1の最左欄に示す化合物を、金属換算で触媒付与液全体に対して、質量で100ppm、表1に含有の指定のあるものは、表1に示すヘテロ環化合物を触媒付与液全体に対して質量で500ppm、表1に含有の指定のあるものは、表1に示すキレート剤を、触媒付与液全体に対して20g/L、となるように純水に溶解させた。次いで表1に示すpHになるよう調整して、各触媒付与液を調製した。pH調整は、pHを上げる時は水酸化ナトリウム水溶液を、下げる時は塩酸を使用した。
実施例1〜6、比較例1〜20で得られた触媒付与液と、公知の無電解還元パラジウムめっき液(ネオパラブライト、日本高純度化学株式会社製)を使用し、表2に示した工程で無電解還元パラジウムめっきを行ない、得られた無電解還元パラジウムめっき皮膜を、それぞれ以下記載の、<無電解還元パラジウムめっきの析出均一性の評価方法>と<微細配線のブリッジの評価方法>にて評価を行なった。
評価基板1
図1及び図2に示した形態の評価基板を作製した。縦40mm×横40mm×厚さ1.0mmのポリイミド樹脂製の基板に、直径0.76mmの円形の銅パッドが碁盤目状に配列されているものであって、各銅パッド周辺がフォトソルダーレジストで被覆されているものを用いた。それぞれの銅パッドは厚さ12μmの銅により形成され、フォトソルダーレジストの厚さは20μm、はんだボールパッドの開口部の直径は0.62mmである。
図3及び図4に示した形態の評価基板を作成した。縦40mm×横40mm×厚さ1.0mmのポリイミド樹脂製の基板に、幅80μm×厚さ40μmの銅配線が幅120μmの間隔をもって配列されているものである。
実施例1〜6、比較例1〜20で得られた触媒付与液及び無電解還元パラジウムめっき液を使用し、上記評価基板1と評価基板2を用いて、以下の表2の処理条件で無電解還元パラジウムめっきを行なった。なお、各触媒付与液による処理条件は、触媒核である金属金の担持量が0.6mg/dm2(0.6×10−5g/cm2)になる条件にて行なった。
評価基板2の銅配線を走査型電子顕微鏡(S−4300、日立製作所製)(以下、「SEM」と略記する)とエネルギー分散型X線分析装置(EMAX EX−220、HORIBA社製)にてパラジウムをマッピング分析することにより、微細配線のブリッジの評価を行なった。
上記の析出均一性評価とブリッジ評価により良好な結果が得られたものに関しては、新たに別の評価基板1を用意して、はんだボール接合時のボイド発生の評価を行なった。下記表3の処理により、ボールパッド上にパラジウムめっき皮膜、次いで金めっき皮膜を形成した評価基板1を、175℃で5時間加熱を行なった。この加熱条件は、基板の実装工程で加わる熱処理を想定したものである。加熱処理後の基板のボールパッドにフラックスを塗布し、直径0.76mmのSn−Ag−Cu鉛フリーはんだボールを搭載し、これをリフロー炉装置(RF−430−M2、株式会社日本パルス技術研究所社製)にて融着させた。
Claims (4)
- 銅系金属の上に0.05〜3mg/dm 2 の金を触媒核金属として付与した後、該銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が2個以上の5員環構造を有するヘテロ環化合物、及び、イミノ2酢酸構造を有するキレート剤を含有する触媒付与液
を用い、銅系金属の上に無電解還元パラジウムめっきを行うことを特徴とする銅系金属上のパラジウムめっき皮膜の製造方法。 - 銅系金属の上に0.05〜3mg/dm 2 の金を触媒核金属として付与した後、該銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が2個以上の5員環構造を有するヘテロ環化合物、及び、イミノ2酢酸構造を有するキレート剤を含有する触媒付与液
を用い、銅系金属の上に無電解還元パラジウムめっきを行って得られたことを特徴とする銅系金属上のパラジウムめっき皮膜。 - 銅系金属の上に0.05〜3mg/dm 2 の金を触媒核金属として付与した後、該銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が2個以上の5員環構造を有するヘテロ環化合物、及び、イミノ2酢酸構造を有するキレート剤を含有する触媒付与液
を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行うことを特徴とする銅系金属上のパラジウム/金めっき皮膜の製造方法。 - 銅系金属の上に0.05〜3mg/dm 2 の金を触媒核金属として付与した後、該銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が2個以上の5員環構造を有するヘテロ環化合物、及び、イミノ2酢酸構造を有するキレート剤を含有する触媒付与液
を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行って得られたことを特徴とする銅系金属上のパラジウム/金めっき皮膜。
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US8591636B2 (en) * | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronics Materials Llc | Plating catalyst and method |
US8591637B2 (en) * | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronic Materials Llc | Plating catalyst and method |
US8965937B2 (en) | 2011-09-28 | 2015-02-24 | International Business Machines Corporation | Automated selection of functions to reduce storage capacity based on performance requirements |
KR20130056629A (ko) * | 2011-11-22 | 2013-05-30 | 삼성전기주식회사 | 기판 및 이의 제조방법 |
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JP6329589B2 (ja) | 2016-06-13 | 2018-05-23 | 上村工業株式会社 | 皮膜形成方法 |
JP6340053B2 (ja) * | 2016-10-05 | 2018-06-06 | 小島化学薬品株式会社 | 無電解パラジウム/金めっきプロセス |
KR102041850B1 (ko) | 2019-04-08 | 2019-11-06 | (주)엠케이켐앤텍 | 인쇄회로기판의 구리표면에 무전해 팔라듐 도금을 실시하기 위한 전처리 공정으로 금스트라이크 도금방법, 도금액 조성물 및 전처리 후의 무전해 팔라듐 도금과 무전해 금도금 방법 |
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