JP2009007656A - Electrolytic gold-plating solution and gold plated film obtained using the same - Google Patents
Electrolytic gold-plating solution and gold plated film obtained using the same Download PDFInfo
- Publication number
- JP2009007656A JP2009007656A JP2007172312A JP2007172312A JP2009007656A JP 2009007656 A JP2009007656 A JP 2009007656A JP 2007172312 A JP2007172312 A JP 2007172312A JP 2007172312 A JP2007172312 A JP 2007172312A JP 2009007656 A JP2009007656 A JP 2009007656A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating solution
- gold plating
- electrolytic
- cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 239000010931 gold Substances 0.000 title claims abstract description 209
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 208
- 238000007747 plating Methods 0.000 title claims abstract description 161
- -1 amine compound Chemical class 0.000 claims abstract description 28
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 22
- 125000001424 substituent group Chemical group 0.000 claims abstract description 18
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000000732 arylene group Chemical group 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 150000003949 imides Chemical class 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 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 claims description 5
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 claims description 5
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 claims description 5
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 4
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 claims description 4
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 4
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- LJJNEPKMBSUEND-UHFFFAOYSA-O azanium;gold;cyanide Chemical compound [NH4+].[Au].N#[C-] LJJNEPKMBSUEND-UHFFFAOYSA-O 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- AXINVSXSGNSVLV-UHFFFAOYSA-N 1h-pyrazol-4-amine Chemical compound NC=1C=NNC=1 AXINVSXSGNSVLV-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005700 Putrescine Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 1
- ITVZBSJBDLFONY-UHFFFAOYSA-N N.[Au](C#N)(C#N)C#N Chemical compound N.[Au](C#N)(C#N)C#N ITVZBSJBDLFONY-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 14
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000151 deposition Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 238000003287 bathing Methods 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000006172 buffering agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 235000015870 tripotassium citrate Nutrition 0.000 description 2
- GOLAKLHPPDDLST-HZJYTTRNSA-N (9z,12z)-octadeca-9,12-dien-1-amine Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCN GOLAKLHPPDDLST-HZJYTTRNSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- MQAAVJSLMCQBIX-UHFFFAOYSA-N C(CCC)C=1C(=C(C2=CC=CC=C2C=1)CCCC)O Chemical compound C(CCC)C=1C(=C(C2=CC=CC=C2C=1)CCCC)O MQAAVJSLMCQBIX-UHFFFAOYSA-N 0.000 description 1
- RRGWLHMMDIOLAD-UHFFFAOYSA-N CCCCCCCCCCCCC(CC([O-])=O)([N+]1=CNC=C1)O Chemical compound CCCCCCCCCCCCC(CC([O-])=O)([N+]1=CNC=C1)O RRGWLHMMDIOLAD-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- KKYNGSVDQZFBIK-UHFFFAOYSA-N N.[Au+3] Chemical group N.[Au+3] KKYNGSVDQZFBIK-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 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
- SJDABMGVYDDHHB-UHFFFAOYSA-N [Au].[Au](C#N)(C#N)C#N Chemical compound [Au].[Au](C#N)(C#N)C#N SJDABMGVYDDHHB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000002648 azanetriyl group Chemical group *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
- 230000015572 biosynthetic process Effects 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
- 235000010338 boric acid Nutrition 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- NHEPKQDGPJQVOO-UHFFFAOYSA-N hex-1-yn-1-amine Chemical compound CCCCC#CN NHEPKQDGPJQVOO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000005649 substituted arylene group Chemical group 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Description
本発明は、電解金めっき液、それを用いて得られた金皮膜及びニッケルめっき皮膜上の金皮膜に関するものである。 The present invention relates to an electrolytic gold plating solution, a gold film obtained by using the electrolytic gold plating solution, and a gold film on a nickel plating film.
ニッケル皮膜上に施す金めっき（以下、「ニッケル／金めっき」と略記する）は、金の優れた耐食性、機械的特性、電気特性等と、ニッケルが下地金属として優れた耐熱性を有するため、電子電気部品等の分野で広く用いられている。ニッケル／金めっきにより析出する金めっき皮膜は大きく分類すると、金純度９９．９％以上で硬度が５０〜８０Ｈｖの純金めっきと、金純度９９．９％未満で硬度が１００Ｈｖ以上の硬質金めっきと呼ばれるものに分けられる。 Gold plating applied to the nickel film (hereinafter abbreviated as “nickel / gold plating”) has excellent corrosion resistance, mechanical characteristics, electrical characteristics, etc. of gold, and nickel has excellent heat resistance as a base metal. Widely used in the field of electronic and electrical parts. Gold plating films deposited by nickel / gold plating can be broadly classified into pure gold plating with a gold purity of 99.9% or more and hardness of 50 to 80 Hv, and hard gold plating with a gold purity of less than 99.9% and hardness of 100 Hv or more. Divided into what is called.
硬質金めっきは、高い硬度と優れた耐摩耗性を生かして、コネクター等の差込部材やスイッチ等の接点部材等のコンタクト接合部として利用されている。しかしながら、硬質金めっきは高い硬度を得るために、コバルトやニッケル等の金属と合金化させるのが一般的であるが、それらの不純物金属が０．１質量％〜１．０質量％程度金皮膜中へ共析するために金純度が低下し、ワイヤーボンディング用には利用できなかった。 Hard gold plating is utilized as a contact joint portion of an insertion member such as a connector or a contact member such as a switch by making use of high hardness and excellent wear resistance. However, hard gold plating is generally alloyed with a metal such as cobalt or nickel in order to obtain high hardness, but the impurity metal is about 0.1% by mass to 1.0% by mass. Since it eutectoidally into the gold, the purity of the gold decreased and it could not be used for wire bonding.
また、硬質金めっきは、はんだ実装に伴う２５０℃前後のリフロー処理によって、硬質金めっき皮膜中に共析しているコバルトやニッケル等の不純物が金めっき皮膜表面で酸化されるため、接触抵抗の上昇が起こりやすく、コネクター等として通電不良を引き起こすという問題があった。 In addition, the hard gold plating has a resistance of contact resistance because impurities such as cobalt and nickel that are co-deposited in the hard gold plating film are oxidized on the surface of the gold plating film by reflow treatment at around 250 ° C. accompanying solder mounting. There is a problem that the rise is likely to occur, causing a poor electrical conduction as a connector or the like.
一方、純金めっきと呼ばれる純度９９．９９質量％以上の金皮膜は、金純度が高いため、ワイヤーボンディング接合用途の表面処理に適しており、リフロー処理における接触抵抗の上昇もないが、軟質であるため接点用途等には利用できなかった。そのため、メモリーカード等、一部の表面処理において、チップとの接続部にはワイヤーボンディング接合性、コンタクト部には接点特性というように、一つのパッケージ内で異なった特性が要求される場合、硬質金めっきと純金めっきとを別々にめっきしなければならない為、生産性が非常に悪いという問題があった。 On the other hand, a gold film with a purity of 99.99% by mass or more called pure gold plating is suitable for surface treatment for wire bonding bonding applications because of its high gold purity, and does not increase contact resistance in reflow treatment, but is soft. Therefore, it could not be used for contact applications. Therefore, in some surface treatments such as memory cards, when different characteristics are required within a single package, such as wire bonding bondability for the chip connection and contact characteristics for the contact, Since gold plating and pure gold plating must be plated separately, there is a problem that productivity is very poor.
この問題を解決するために、金めっき皮膜中にコバルトやニッケルの共析を防ぐために、非水溶媒を用いて、従来の酸性浴金めっきと同等以上の性能を有する金皮膜が得られる金めっき浴が特許文献１に開示されているが、従来、電析浴の溶媒には水が使用されており、排水設備を新設しなければならない等、実用的ではなかった。 In order to solve this problem, a gold film that has a performance equal to or better than that of conventional acid bath gold plating can be obtained by using a non-aqueous solvent to prevent the eutectoid of cobalt and nickel in the gold plating film. Although the bath is disclosed in Patent Document 1, conventionally, water has been used as the solvent for the electrodeposition bath, and it has not been practical because a drainage facility has to be newly installed.
また、ニッケル及びコバルトを硬化剤として含有するが、同時に脂肪族アルコールを含有させることにより、金めっき後にリフロー処理を行っても、接触抵抗値が上昇しないという金めっき浴が特許文献２に開示されているが、金皮膜にコバルトやニッケルが共析している以上、リフロー処理でのニッケルやコバルトの酸化による接触抵抗の上昇を抑制することには限界があり、根本的な解決には至っていない。また、金皮膜中にコバルトやニッケルの共析があるために、ワイヤーボンディング用には使用できなかった。 Further, Patent Document 2 discloses a gold plating bath that contains nickel and cobalt as a curing agent, but at the same time contains an aliphatic alcohol so that the contact resistance value does not increase even if reflow treatment is performed after gold plating. However, as long as cobalt and nickel are co-deposited in the gold film, there is a limit to suppressing the increase in contact resistance due to oxidation of nickel and cobalt during reflow treatment, and no fundamental solution has been reached. . Further, since there is a eutectoid of cobalt and nickel in the gold film, it cannot be used for wire bonding.
更に、電析硬質金浴として、硬化剤としてニッケルやコバルトを含有させずに、アミン類を含有させる金めっき浴が、特許文献３に開示されているが、めっき浴の使用が進んでくると、めっき浴中の１価の金が、３価の金に酸化され、析出効率が低下して、析出速度が変化し、安定した析出速度が得られなくなるため、実用的ではなかった。 Furthermore, as an electrodeposition hard gold bath, a gold plating bath containing amines without containing nickel or cobalt as a curing agent is disclosed in Patent Document 3, but when the use of the plating bath proceeds Since the monovalent gold in the plating bath is oxidized to trivalent gold, the deposition efficiency is lowered, the deposition rate is changed, and a stable deposition rate cannot be obtained, which is not practical.
本発明は上記背景技術に鑑みてなされたものであり、その課題は、ランニングにおいて析出効率の低下がなく、金皮膜が硬質で金純度が９９．９％以上である金皮膜が得られる電解金めっき液を提供することである。また、上記電解金めっき液を用いることにより、ワイヤーボンディングパッドとコンタクト接合部の両方に、同一組成、同一物性の金皮膜が施された電子部品を提供することにある。 The present invention has been made in view of the above-mentioned background art, and the problem is that electrolytic gold is obtained in which a gold film having a hard gold film and a gold purity of 99.9% or more is obtained without a decrease in precipitation efficiency during running. It is to provide a plating solution. Another object of the present invention is to provide an electronic component in which a gold film having the same composition and the same physical properties is applied to both the wire bonding pad and the contact bonding portion by using the electrolytic gold plating solution.
本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、シアン化金塩と特定のアミン化合物及び特定の複素環式化合物を含有する電解金めっき液を用いて金皮膜を形成すれば、金皮膜の硬度が１００Ｈｖ以上であり、金純度が９９．９％以上で、金めっき後にリフロー処理をしても接触抵抗が上昇しない金皮膜が得られ、金めっき液のランニング中において析出効率の低下がなく、安定した製品製造ができることを見出し、本発明の完成に至った。 As a result of intensive studies to solve the above problems, the present inventor formed a gold film using an electrolytic gold plating solution containing a gold cyanide salt, a specific amine compound and a specific heterocyclic compound. For example, the hardness of the gold film is 100 Hv or more, the gold purity is 99.9% or more, and a gold film that does not increase contact resistance even after reflow treatment after gold plating is obtained. The present inventors have found that there is no reduction in efficiency and that a stable product can be produced, and the present invention has been completed.
すなわち本発明は、シアン化金塩を金源とし、下記式（１）で示されるアミン化合物及び下記式（３）で示される複素環式化合物を含有していることを特徴とする電解金めっき液を提供するものである。
Ｈ２Ｎ−（Ｒ１−ＮＨ）ｎ−Ｈ （１）
［式（１）中、Ｒ１は置換基を有していてもよい炭素数１〜１２の、アルキレン基、アリーレン基若しくはアルキレンアリーレン基を示し、ｎは１以上の自然数である。］
H 2 N- (R 1 -NH) n -H (1)
[In Formula (1), R 1 represents an alkylene group, an arylene group or an alkylene arylene group having 1 to 12 carbon atoms which may have a substituent, and n is a natural number of 1 or more. ]
また本発明は、更に、下記式（２）で示されるスルホン酸又はその塩を含有している上記の電解金めっき液を提供するものである。
ＨａＮ−（ＳＯ３Ｘ）ｂ （２）
［式（２）中、ｘはＨ、Ｎａ、Ｋ又はＮＨ４を示し、ａは０、１又は２であり、ｂは１、２又は３であり、ａ＋ｂ＝３である。］
The present invention further provides the electrolytic gold plating solution containing a sulfonic acid represented by the following formula (2) or a salt thereof.
H a N- (SO 3 X) b (2)
[In the formula (2), x represents H, Na, K or NH 4 , a is 0, 1 or 2, b is 1, 2 or 3, and a + b = 3. ]
また本発明は、上記の電解金めっき液を用いて電解金めっきを行うことによって得られたことを特徴とする金皮膜を提供するものである。 The present invention also provides a gold film obtained by performing electrolytic gold plating using the above electrolytic gold plating solution.
また本発明は、上記の電解金めっき液を用いて作製されたワイヤーボンディングパッド及びコンタクト接合部の何れにも使用可能な金皮膜を提供するものである。 The present invention also provides a gold film that can be used for both the wire bonding pad and the contact bonding portion produced by using the electrolytic gold plating solution.
また本発明は、上記の電解金めっき液を用いて、同時に１回の電解金めっきを行うことによって製造された、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品を提供するものである。 Moreover, this invention provides the electronic component which has both the wire bonding pad and the contact junction part in the same board | substrate manufactured by performing electrolytic gold plating once simultaneously using said electrolytic gold plating solution. Is.
同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品であって、該ワイヤーボンディングパッドと該コンタクト接合部が、同一の金純度で同一のビッカース硬度を有する金皮膜が施されているものであることを特徴とする電子部品を提供するものである。 An electronic component having both a wire bonding pad and a contact bonding portion in the same substrate, wherein the wire bonding pad and the contact bonding portion are provided with a gold film having the same gold purity and the same Vickers hardness. The present invention provides an electronic component characterized by being a thing.
本発明によれば、金めっき後にリフロー処理をしても、接触抵抗の上昇がないので、コネクターの接点部分、コンタクト接合部の通電不良を防止でき、金の純度が高いことからワイヤーボンディング用に利用でき、電解金めっき液でのランニング中に３価の金の生成が抑制されており、電解金めっき液の析出効率も低下しないため、長期にわたり安定な製造が可能な電解金めっき液が得られる。また、ニッケル皮膜上に本発明の電解金めっきを行うことによって得られたニッケル皮膜上の金皮膜は、金の純度が高く、硬質なため非常に有用である。更に、本発明によれば、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品を、同時に１回の電解金めっきを行うことによって製造することが可能となる。 According to the present invention, even if reflow treatment is performed after gold plating, there is no increase in contact resistance. Therefore, it is possible to prevent poor current conduction in the contact portion of the connector and the contact joint portion, and for gold bonding because the purity of gold is high. It can be used, and the generation of trivalent gold is suppressed during running with the electrolytic gold plating solution, and the deposition efficiency of the electrolytic gold plating solution is not lowered, so that an electrolytic gold plating solution that can be manufactured stably for a long time is obtained. It is done. Further, the gold film on the nickel film obtained by performing the electrolytic gold plating of the present invention on the nickel film is very useful because it has high gold purity and is hard. Furthermore, according to the present invention, it is possible to manufacture an electronic component having both a wire bonding pad and a contact bonding portion in the same substrate by performing electrolytic gold plating once at the same time.
以下、本発明について説明するが、本発明は以下の実施の具体的形態に限定されるものではなく、技術的思想の範囲内で任意に変形することができる。 Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.
本発明は、シアン化金塩を金源とし、下記式（１）で示されるアミン化合物及び下記式（３）で示される複素環式化合物を含有する電解金めっき液に係るものである。
Ｈ２Ｎ−（Ｒ１−ＮＨ）ｎ−Ｈ （１）
［式（１）中、Ｒ１は置換基を有していてもよい炭素数１〜１２の、アルキレン基、アリーレン基若しくはアルキレンアリーレン基を示し、ｎは１以上の自然数である。］
H 2 N- (R 1 -NH) n -H (1)
[In Formula (1), R 1 represents an alkylene group, an arylene group or an alkylene arylene group having 1 to 12 carbon atoms which may have a substituent, and n is a natural number of 1 or more. ]
本発明の電解金めっき液は、シアン化金塩を含有することが必須である。該シアン化金塩は、本発明の電解金めっき液の金源として用いられる。ここで「シアン化金塩」とは、「シアン化金酸塩」、「テトラシアノ金酸塩」と同義である。シアン化金塩は１種の使用に限定されず２種以上を併用することができる。 The electrolytic gold plating solution of the present invention must contain a gold cyanide salt. The gold cyanide salt is used as a gold source for the electrolytic gold plating solution of the present invention. Here, “gold cyanide salt” is synonymous with “gold cyanide salt” and “tetracyanoaurate salt”. The gold cyanide salt is not limited to one type, and two or more types can be used in combination.
該シアン化金塩としては、金の供給源となるものであれば特に限定はないが、シアン化第１金塩及びシアン化第２金塩からなる群より選ばれるものであることが好ましい。該シアン化金塩の金の価数（酸化数）としては、１価又は３価のどちらでも使用可能であるが、金の析出速度の観点から１価が好ましい。すなわちシアン化第１金塩が好ましい。 The gold cyanide salt is not particularly limited as long as it is a gold supply source, but is preferably selected from the group consisting of a first gold cyanide salt and a second gold cyanide salt. As the gold valence (oxidation number) of the gold cyanide salt, either monovalent or trivalent can be used, but monovalent is preferable from the viewpoint of the deposition rate of gold. That is, the first cyanide gold salt is preferable.
該シアン化金塩の具体例としては、例えば、シアン化第１金ナトリウム、シアン化第１金カリウム、シアン化第１金アンモニウム、シアン化第２金ナトリウム、シアン化第２金カリウム、シアン化第２金アンモニウム等が挙げられる。これらのうち、上記析出速度、めっき性能、コスト及び入手が容易である点から、シアン化第１金ナトリウム又はシアン化第１金カリウムが好ましい。 Specific examples of the gold cyanide salt include, for example, first gold sodium cyanide, first gold potassium cyanide, first gold ammonium cyanide, second gold sodium cyanide, second gold potassium cyanide, cyanide. Secondary gold ammonium and the like can be mentioned. Among these, from the above-mentioned precipitation rate, plating performance, cost, and easy availability, 1st gold sodium cyanide or 1st gold potassium cyanide is preferable.
本発明の電解金めっき液中の該シアン化金塩の含有量は特に限定はないが、電解金めっき液全体に対して金属金として、通常０．５ｇ／Ｌ〜１００ｇ／Ｌ、好ましくは２ｇ／Ｌ〜５０ｇ／Ｌ、特に好ましくは５ｇ／Ｌ〜３０ｇ／Ｌである。電解金めっき液中の金属金の含有量が少なすぎると、金皮膜の析出速度が遅く実用的でない場合があり、また、電解金めっき液中の金属金の含有量が多すぎると、金源としてのシアン化金塩の溶解が難しい場合がある。 The content of the gold cyanide salt in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 0.5 g / L to 100 g / L, preferably 2 g as metal gold with respect to the entire electrolytic gold plating solution. / L to 50 g / L, particularly preferably 5 g / L to 30 g / L. If the amount of metal gold in the electrolytic gold plating solution is too small, the deposition rate of the gold film may be slow and may not be practical, and if the content of metal gold in the electrolytic gold plating solution is too high, It may be difficult to dissolve the gold cyanide salt.
上記のシアン化金塩についての記載は、本発明の電解金めっき液中に存在する形態を特定するものであるが、本発明の電解金めっき液の調液の際に、溶解させる原料として、上記のシアン化金塩を用いることも好ましい。 The description about the above gold cyanide salt specifies the form present in the electrolytic gold plating solution of the present invention, but as a raw material to be dissolved in the preparation of the electrolytic gold plating solution of the present invention, It is also preferable to use the above gold cyanide salt.
本発明の電解金めっき液には、上記式（１）で示されるアミン化合物及び上記式（３）で示される複素環式化合物を含有することが必須である。これらの両方を含有させることによって、電解金めっき液の析出効率も低下せず、金純度が高く、硬質な金皮膜が得られる。 It is essential for the electrolytic gold plating solution of the present invention to contain an amine compound represented by the above formula (1) and a heterocyclic compound represented by the above formula (3). By including both of these, the deposition efficiency of the electrolytic gold plating solution is not lowered, and a gold film having a high gold purity and a high hardness can be obtained.
上記式（１）で示されるアミン化合物において、ｎは１以上の自然数を示すが、１〜１２の範囲の自然数が好ましく、特に好ましくは１〜５の自然数である。 In the amine compound represented by the above formula (1), n represents a natural number of 1 or more, but a natural number in the range of 1 to 12 is preferable, and a natural number of 1 to 5 is particularly preferable.
上記式（１）中、Ｒ１は置換基を有していてもよい炭素数１〜１２の、アルキレン基、アリーレン（arylene）基若しくはアルキレンアリーレン基を示す。ここで、炭素数は好ましくは１〜１０個、より好ましくは２〜８個、特に好ましくは２〜５個である。炭素数が多すぎると、メッキ浴への溶解速度が遅くなり作業性が低下する場合があり、また、入手しにくく、時間が経過すると個体に変わってしまい取り扱いが不便となる場合がある。 In the above formula (1), R 1 represents an alkylene group, an arylene group or an alkylene arylene group having 1 to 12 carbon atoms which may have a substituent. Here, the number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 5. If the number of carbon atoms is too large, the dissolution rate in the plating bath may be slowed and workability may be reduced, and it may be difficult to obtain and may change to an individual over time, resulting in inconvenience in handling.
「置換基を有していてもよい炭素数１〜１２のアルキレン基」としては、−ＣｍＨ２ｍ−（ｍは１〜１２の自然数）で表される側鎖を有してもよいアルキレン基、すなわち、−ＣｍＨ２ｍ−（ｍは１〜１２の自然数）で表される直鎖構造でも側鎖構造でもよいアルキレン基等が挙げられる。これらは置換基を有していてもよい。 The “alkylene group having 1 to 12 carbon atoms which may have a substituent” is an alkylene which may have a side chain represented by —C m H 2m — (m is a natural number of 1 to 12). And an alkylene group which may be a linear structure or a side chain structure represented by a group, that is, —C m H 2m — (m is a natural number of 1 to 12). These may have a substituent.
また、「置換基を有していてもよい炭素数１〜１２のアリーレン基」としては、フェニレン基、ナフチレン基等が挙げられる。これらは置換基を有していてもよい。 Examples of the “optionally substituted arylene group having 1 to 12 carbon atoms” include a phenylene group and a naphthylene group. These may have a substituent.
また、「置換基を有していてもよい炭素数１〜１２のアルキレンアリーレン基」としては、上記したアルキレン基とアリーレン基が結合した基が挙げられる。これらは置換基を有していてもよい。 Examples of the “optionally substituted alkylene arylene group having 1 to 12 carbon atoms” include groups in which the alkylene group and the arylene group described above are bonded. These may have a substituent.
上記式（１）中、Ｒ１のアルキレン基、アリーレン基、アルキレンアリーレン基の置換基としては、アルキル基等が挙げられる。 In the above formula (1), examples of the substituent for the alkylene group, arylene group, and alkylene arylene group represented by R 1 include an alkyl group.
式（１）で示されるアミン化合物の好ましい具体例としては、例えば、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン、１，１１−ジアミノウンデカン、１，１２−ジアミノドデカン、１，２−フェニレンジアミン、１，３−フェニレンジアミン、１，４−フェニレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、２−メチル−１，５−ジアミノペンタン等が挙げられる。これらのアミン化合物は、めっき性能、入手のしやすさ等の点で好ましい。また、式（３）で示される複素環式化合物との相乗効果として、析出効率が低下せず、金純度が高くても硬質な金皮膜が得られる。これらのアミン化合物は、１種又は２種以上を混合して用いることができる。 Preferable specific examples of the amine compound represented by the formula (1) include, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-phenylenediamine, 1,3- Examples include phenylenediamine, 1,4-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 2-methyl-1,5-diaminopentane and the like. These amine compounds are preferable in terms of plating performance, availability, and the like. Moreover, as a synergistic effect with the heterocyclic compound represented by the formula (3), the deposition efficiency does not decrease, and a hard gold film can be obtained even if the gold purity is high. These amine compounds can be used alone or in combination of two or more.
本発明の電解金めっき液中の上記式（１）で示されるアミン化合物の含有量は特に限定はないが、電解金めっき液全体に対して、通常０．０１ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは０．１ｇ／Ｌ〜２００ｇ／Ｌ、より好ましくは０．５ｇ／Ｌ〜１００ｇ／Ｌ、特に好ましくは１ｇ／Ｌ〜５０ｇ／Ｌである。電解金めっき液中に上記式（１）で示されるアミン化合物の含有量が少なすぎると、本発明の上記効果を充分に奏さない場合があり、また、電気伝導度上昇の効果を発揮しない場合があり、また、多すぎると水に溶解し難い、電気伝導度の更なる上昇の効果は見られず不経済等の問題が生じる場合がある。 The content of the amine compound represented by the above formula (1) in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 0.01 g / L to 500 g / L with respect to the entire electrolytic gold plating solution, preferably Is 0.1 g / L to 200 g / L, more preferably 0.5 g / L to 100 g / L, and particularly preferably 1 g / L to 50 g / L. When the content of the amine compound represented by the above formula (1) is too small in the electrolytic gold plating solution, the above effect of the present invention may not be sufficiently achieved, and the effect of increasing the electrical conductivity may not be exhibited. In addition, if it is too much, it is difficult to dissolve in water, and the effect of further increase in electrical conductivity is not seen, and problems such as uneconomics may occur.
上記式（３）で示される複素環式化合物において、Ｎを含む環は、環中にＮを２個以上有する複素環を示し、該複素環中の炭素原子には置換基が結合していてもよい。すなわち、かかる複素環は、環中に窒素原子（Ｎ）を２個以上有し、その窒素原子（Ｎ）のうちの少なくとも１つには水素原子（Ｈ）が結合して、−ＮＨ−なる構造を有しているものである。複素環には、１つの環で構成されているものも、２つ以上の環で構成されているものも含まれる。複素環が２つ以上の環で構成されている場合、複素環全体に窒素原子（Ｎ）を２個以上有していればよく、複素環中の１つの環に窒素原子（Ｎ）を２個以上有している必要はないが、複素環中の１つの環に窒素原子（Ｎ）を２個以上有していることが好ましい。かかる化合物は、金の酸化防止作用があり、原子価３価の金の生成が抑制され、原子価１価と３価の金の比率が変動することがなく、金めっき液の析出効率の低下がほとんどない金皮膜が得られる。また、式（１）で示されるアミン化合物と併用することによって、析出効率が低下せず、金純度が高くても硬質な金皮膜を与える電解金メッキ液が得られる。 In the heterocyclic compound represented by the above formula (3), a ring containing N represents a heterocyclic ring having two or more N in the ring, and a substituent is bonded to a carbon atom in the heterocyclic ring. Also good. That is, the heterocyclic ring has two or more nitrogen atoms (N) in the ring, and at least one of the nitrogen atoms (N) is bonded to a hydrogen atom (H) to form —NH—. It has a structure. Heterocycles include those composed of one ring and those composed of two or more rings. When the heterocyclic ring is composed of two or more rings, it suffices if the entire heterocyclic ring has two or more nitrogen atoms (N), and one nitrogen in the heterocyclic ring has two nitrogen atoms (N). It is not necessary to have more than one, but it is preferable to have two or more nitrogen atoms (N) in one ring in the heterocycle. Such a compound has an antioxidant effect on gold, suppresses the formation of trivalent gold, prevents the ratio of monovalent to trivalent gold from changing, and decreases the deposition efficiency of the gold plating solution. A gold film with almost no is obtained. Moreover, by using together with the amine compound shown by Formula (1), the electrolysis gold plating liquid which gives a hard gold film, even if gold purity is high without precipitation efficiency falling is obtained.
該複素環としては、π電子過剰複素環であることが好ましい。「π電子過剰複素環」の定義については、成書“Heterocyclic Chemistry, by Adrien Albert, The Anthon Press University of London,1959”に詳細に記載されている。具体的には、例えば、ピラゾール環、イミダゾール環、１，２，３−トリアゾール環、１，２，４−トリアゾール環、テトラゾール環、ベンズイミダゾール環、ベンズトリアゾール環等が挙げられる。上記式（３）で示される複素環式化合物としては、π電子過剰複素環式化合物が、金の酸化防止作用があるため好ましい。また、式（１）で示されるアミン化合物との相乗効果として、析出効率が低下せず、金純度が高くても硬質な金皮膜が得られる。 The heterocyclic ring is preferably a π-electron rich heterocyclic ring. The definition of “π-electron rich heterocycle” is described in detail in the book “Heterocyclic Chemistry, by Adrien Albert, The Anthon Press University of London, 1959”. Specific examples include a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a benzimidazole ring, and a benztriazole ring. As the heterocyclic compound represented by the above formula (3), a π-electron rich heterocyclic compound is preferable since it has an antioxidant effect on gold. Further, as a synergistic effect with the amine compound represented by the formula (1), the deposition efficiency does not decrease, and a hard gold film can be obtained even if the gold purity is high.
該複素環中の炭素原子には置換基が結合していてもよい。かかる置換基としては特に限定はないが、例えば、アルキル基、シクロアルキル基、水酸基、アルコキシル基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アミノアルキル基等が挙げられる。これらの中でもアミノ基等が好ましい。 A substituent may be bonded to the carbon atom in the heterocyclic ring. The substituent is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, and an aminoalkyl group. Among these, an amino group and the like are preferable.
式（３）で表わされる複素環式化合物の好ましい具体例としては、例えば、３−アミノピラゾール、４−アミノピラゾール、５−アミノピラゾール、２−アミノイミダゾール、４−アミノイミダゾール、５−アミノイミダゾール、１，２，３トリアゾール、４−アミノ−１，２，３−トリアゾール、５−アミノ−１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、５−アミノ−１，２，４−トリアゾール、ベンゾトリアゾール、５−メチルベンゾトリアゾール、テトラゾール、５−アミノテトラゾール、２−アミノベンズイミダソール、ベンズイミダゾール等が挙げられる。これらの複素環式化合物は、１種又は２種以上を混合して用いることができる。 Preferable specific examples of the heterocyclic compound represented by the formula (3) include, for example, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, 2-aminoimidazole, 4-aminoimidazole, 5-aminoimidazole, 1,2,3 triazole, 4-amino-1,2,3-triazole, 5-amino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole , 5-amino-1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, tetrazole, 5-aminotetrazole, 2-aminobenzimidazole, benzimidazole and the like. These heterocyclic compounds can be used alone or in combination of two or more.
本発明の電解金めっき液中の式（３）で示される複素環式化合物の含有量は、電解金めっき液全体に対して、通常０．０１ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは０．０５ｇ／Ｌ〜１００ｇ／Ｌ、より好ましくは０．１ｇ／Ｌ〜５０ｇ／Ｌであり、特に好ましくは０．５ｇ／Ｌ〜２０ｇ／Ｌである。電解金めっき液中に上記式（３）で示される複素環式化合物の含有量が少なすぎると、本発明の上記効果を充分に奏さない場合があり、また、電気伝導度上昇の効果を発揮しない場合があり、また、多すぎると水に溶解し難い、電気伝導度の更なる上昇の効果は見られず不経済等の問題が生じる場合がある。 The content of the heterocyclic compound represented by the formula (3) in the electrolytic gold plating solution of the present invention is usually 0.01 g / L to 500 g / L, preferably 0.05 g, based on the entire electrolytic gold plating solution. / L to 100 g / L, more preferably 0.1 g / L to 50 g / L, and particularly preferably 0.5 g / L to 20 g / L. If the content of the heterocyclic compound represented by the above formula (3) is too small in the electrolytic gold plating solution, the above effect of the present invention may not be sufficiently exerted, and the effect of increasing electrical conductivity is exhibited. If the amount is too large, it may be difficult to dissolve in water, and the effect of further increasing the electrical conductivity may not be seen, resulting in problems such as uneconomical issues.
本発明の電解金メッキには、更に、下記式（２）で示されるスルホン酸又はその塩が含有されていることが好ましい。
ＨａＮ−（ＳＯ３Ｘ）ｂ （２）
［式（２）中、ｘはＨ、Ｎａ、Ｋ又はＮＨ４を示し、ａは０、１又は２であり、ｂは１、２又は３であり、ａ＋ｂ＝３である。］
The electrolytic gold plating of the present invention preferably further contains a sulfonic acid represented by the following formula (2) or a salt thereof.
H a N- (SO 3 X) b (2)
[In the formula (2), x represents H, Na, K or NH 4 , a is 0, 1 or 2, b is 1, 2 or 3, and a + b = 3. ]
本発明における上記式（２）で示されるスルホン酸又はその塩としては、具体的には、例えば、アミドスルホン酸、イミドスルホン酸、ニトリロスルホン酸、前記３種のアルカリ金属塩、アンモニウム塩等が挙げられる。電解金めっきの性能、入手の容易さの点で、アミドスルホン酸アンモニウム、アミドスルホン酸ナトリウム、アミドスルホン酸カリウム、イミドスルホン酸アンモニウム、イミドスルホン酸ナトリウム、イミドスルホン酸カリウム、ニトリロスルホン酸アンモニウム、ニトリロスルホン酸ナトリウム又はニトリロスルホン酸カリウムが好ましい。これらのスルホン酸又はその塩は、１種又は２種以上を混合して用いることができる。 Specific examples of the sulfonic acid represented by the above formula (2) or a salt thereof in the present invention include, for example, amide sulfonic acid, imide sulfonic acid, nitrilosulfonic acid, the above three alkali metal salts, ammonium salts, and the like. Can be mentioned. In terms of the performance and availability of electrolytic gold plating, ammonium amide sulfonate, sodium amide sulfonate, potassium amide sulfonate, ammonium imide sulfonate, sodium imide sulfonate, potassium imide sulfonate, ammonium nitrilosulfonate, nitrilo Sodium sulfonate or potassium nitrilosulfonate is preferred. These sulfonic acids or salts thereof can be used alone or in combination.
本発明の電解金めっき液中の上記式（２）で示されるスルホン酸又はその塩の含有量は特に限定はないが、電解金めっき液全体に対して、通常０ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは０．５ｇ／Ｌ〜２００ｇ／Ｌ、より好ましくは２ｇ／Ｌ〜１００ｇ／Ｌ、特に好ましくは５ｇ／Ｌ〜５０ｇ／Ｌである。電解金めっき液中の上記式（２）で示されるスルホン酸又はその塩の含有量が少なすぎると、電気伝導度上昇の効果を発揮しない場合があり、また、多すぎると水に溶解し難い、電気伝導度の更なる上昇の効果は見られず不経済等の問題が生じる場合がある。 The content of the sulfonic acid represented by the above formula (2) or the salt thereof in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 0 g / L to 500 g / L with respect to the entire electrolytic gold plating solution, Preferably they are 0.5 g / L-200 g / L, More preferably, they are 2 g / L-100 g / L, Especially preferably, they are 5 g / L-50 g / L. If the content of the sulfonic acid represented by the above formula (2) or its salt in the electrolytic gold plating solution is too small, the effect of increasing the electrical conductivity may not be exhibited, and if too much, it is difficult to dissolve in water. However, the effect of further increase in electrical conductivity is not seen, and problems such as uneconomics may occur.
本発明の電解金めっき液は、上記成分以外にも必要に応じて、電解金めっき液のｐＨを一定に保つための緩衝剤、金めっき皮膜のピンホール除去若しくはめっき液の泡切れを良好にするための界面活性剤等を含有させて使用することができる。 In addition to the above components, the electrolytic gold plating solution of the present invention, as necessary, is a buffer for keeping the pH of the electrolytic gold plating solution constant, removes pinholes from the gold plating film, or removes bubbles from the plating solution. It can be used by containing a surfactant or the like.
本発明の電解金めっき液に必要に応じて含有される緩衝剤としては、周知の緩衝剤であれば特に限定はないが、ホウ酸、リン酸等の無機酸、クエン酸、酒石酸、リンゴ酸等のオキシカルボン酸等が挙げられる。これらは１種又は２種以上を混合して用いることができる。 The buffering agent contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known buffering agent. However, inorganic acids such as boric acid and phosphoric acid, citric acid, tartaric acid, malic acid And oxycarboxylic acids such as These may be used alone or in combination of two or more.
本発明の電解金めっき液中の緩衝剤の含有量は特に限定はないが、通常１ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは１０ｇ／Ｌ〜１００ｇ／Ｌである。電解金めっき液中の緩衝剤の含有量が少なすぎると、緩衝効果が発揮され難い場合があり、一方、多すぎる場合は緩衝効果の上昇が見られず不経済の場合がある。 The content of the buffer in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 1 g / L to 500 g / L, preferably 10 g / L to 100 g / L. If the content of the buffering agent in the electrolytic gold plating solution is too small, the buffering effect may be difficult to be exhibited. On the other hand, if the content is too large, the buffering effect may not be increased and it may be uneconomical.
本発明の電解金めっき液に必要に応じて含有される界面活性剤としては、周知の界面活性剤であれば特に限定はなく、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤又は両性界面活性剤が用いられる。これらは１種又は２種以上を混合して用いることができる。 The surfactant contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known surfactant, and is a nonionic surfactant, an anionic surfactant, a cationic surfactant. Agents or amphoteric surfactants are used. These may be used alone or in combination of two or more.
ノニオン系界面活性剤としては、ノニフェノールポリアルコキシレート、α−ナフトールポリアルコキシレート、ジブチル−β−ナフトールポリアルコキシレート、スチレン化フェノールポリアルコキシレート等のエーテル型ノニオン系界面活性剤；オクチルアミンポリアルコキシレート、ヘキシニルアミンポリアルコキシレート、リノレイルアミンポリアルコキシレート等のアミン型ノニオン系界面活性剤等が挙げられる。 Nonionic surfactants include ether type nonionic surfactants such as noniphenol polyalkoxylate, α-naphthol polyalkoxylate, dibutyl-β-naphthol polyalkoxylate, styrenated phenol polyalkoxylate; octylamine polyalkoxy Examples thereof include amine-type nonionic surfactants such as rate, hexynylamine polyalkoxylate, and linoleylamine polyalkoxylate.
アニオン系界面活性剤としては、ラウリル硫酸ナトリウム等のアルキル硫酸塩；ポリオキシエチレンノニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸塩；ポリオキシエチレンアルキルフェニルエーテル硫酸塩；アルキルベンゼンスルホン酸塩等が挙げられる。 Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene nonyl ether sulfate; polyoxyethylene alkyl phenyl ether sulfates; It is done.
カチオン界面活性剤としては、ラウリルトリメチルアンモニウム塩、ラウリルジメチルアンモニウムベタイン、ラウリルピリジニウム塩、オレイルイミダゾリウム塩、ステアリルアミンアセテート等が挙げられる。 Examples of the cationic surfactant include lauryl trimethyl ammonium salt, lauryl dimethyl ammonium betaine, lauryl pyridinium salt, oleyl imidazolium salt, stearyl amine acetate and the like.
両性界面活性剤としては、２−ウンデシル−１−カルボキシメチル−１−ヒドロキシエチルイミダゾリウムベタイン、Ｎ−ステアリル−Ｎ，Ｎ−ジメチル−Ｎ−カルボキシメチルベタイン、ラウリルジメチルアミンオキシド等が挙げられる。 Examples of amphoteric surfactants include 2-undecyl-1-carboxymethyl-1-hydroxyethylimidazolium betaine, N-stearyl-N, N-dimethyl-N-carboxymethylbetaine, lauryldimethylamine oxide, and the like.
これらは１種又は２種以上を混合して用いることができるが、好ましくはノニオン系界面活性剤又は両性界面活性剤である。 These can be used alone or in combination of two or more, but are preferably nonionic surfactants or amphoteric surfactants.
本発明の電解金めっき液中の界面活性剤の含有量は、好ましくは０．０１ｇ／Ｌ〜２０ｇ／Ｌであるが、所望の性能を発揮すればよく、特に含有量を限定するものではない。 The content of the surfactant in the electrolytic gold plating solution of the present invention is preferably 0.01 g / L to 20 g / L. However, the content is not particularly limited as long as the desired performance is exhibited. .
上記した本発明の電解金めっき液のめっき条件は特に限定されるものではないが、温度条件としては、２０℃〜８０℃であることが好ましく、特に好ましくは２５℃〜６０℃である。また、めっき液のｐＨはｐＨ２．０〜ｐＨ９．０であることが好ましく、特に好ましいのは、ｐＨ３．０〜ｐＨ８．０である。また、陰極電流密度は、０．１Ａ／ｄｍ２〜１０Ａ／ｄｍ２であることが好ましく、特に好ましくは０．３Ａ／ｄｍ２〜５Ａ／ｄｍ２である。 Although the plating conditions of the electrolytic gold plating solution of the present invention described above are not particularly limited, the temperature conditions are preferably 20 ° C. to 80 ° C., particularly preferably 25 ° C. to 60 ° C. The pH of the plating solution is preferably pH 2.0 to pH 9.0, and particularly preferably pH 3.0 to pH 8.0. The cathode current density is preferably from 0.1A / dm 2 ~10A / dm 2 , particularly preferably from 0.3A / dm 2 ~5A / dm 2 .
本発明の電解金めっき液を用いて電解めっきを行うことによって得られる金皮膜の膜厚に特に限定はないが、好ましくは０．０１μｍ〜２０μｍ、特に好ましくは０．０５μｍ〜５μｍである。 Although there is no limitation in particular in the film thickness of the gold film obtained by performing electroplating using the electrolytic gold plating solution of this invention, Preferably it is 0.01 micrometer-20 micrometers, Most preferably, it is 0.05 micrometer-5 micrometers.
本発明の電解金めっき液を用いて電解金めっきを行なうときは、下地めっき処理としてニッケルめっき皮膜を形成させておくことが好ましい。このときのニッケルめっき液は特に限定されるものではないが、一般に実用されているワット浴、スルファミン浴、臭化ニッケル浴等が好適である。また、使用するニッケルめっき液にピット防止剤、１次光沢剤又は２次光沢剤を必要に応じて添加して用いることができる。ニッケルめっき浴の使用方法は、特に限定はなく定法に従って使用する。 When performing electrolytic gold plating using the electrolytic gold plating solution of the present invention, it is preferable to form a nickel plating film as a base plating treatment. The nickel plating solution at this time is not particularly limited, but a watt bath, a sulfamine bath, a nickel bromide bath or the like that is generally used is suitable. Moreover, a pit inhibitor, a primary brightener, or a secondary brightener can be added to the nickel plating solution to be used as necessary. The method of using the nickel plating bath is not particularly limited and is used according to a standard method.
ニッケルめっき皮膜の膜厚も特に限定されるものではないが、０．５μｍ〜２０μｍであることが好ましく、特に好ましくは１μｍ〜１０μｍである。 The thickness of the nickel plating film is not particularly limited, but is preferably 0.5 μm to 20 μm, and particularly preferably 1 μm to 10 μm.
本発明の電解金めっき液を用いて電解金めっきを行なうと、その金皮膜は、リフロー処理をしても接触抵抗の上昇がないので、コネクター等コンタクト接合部の通電不良を防止でき、また、金の純度が高いのでワイヤーボンディング用にも使用可能である。すなわち、本発明の電解金めっき液を用いて電解金めっきを行なうことによって、ワイヤーボンディングパッド及びコンタクト接合部の何れにも使用可能な金皮膜を得ることができる。 When electrolytic gold plating is performed using the electrolytic gold plating solution of the present invention, the gold film does not increase in contact resistance even after reflow treatment, so that it is possible to prevent poor conduction of contact joints such as connectors, Since the purity of gold is high, it can also be used for wire bonding. That is, by performing electrolytic gold plating using the electrolytic gold plating solution of the present invention, a gold film that can be used for both the wire bonding pad and the contact bonding portion can be obtained.
また、本発明の電解金めっき液を用いることによって、同時に１回の電解金めっきで、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品を製造することができ、コスト的に有利である。メモリーカード等においては、チップとの接続部にはワイヤーボンディングパッドがあり、コンタクト接合部も一つのパッケージ内にある場合、硬質金めっきと純金めっきとを別々にめっきしなくてもよいので、生産性が非常に良い。従って、本発明の別の態様は、本発明の電解金めっき液を用いて、同時に１回の電解金めっきを行うことによって製造された、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品に係るものである。 In addition, by using the electrolytic gold plating solution of the present invention, an electronic component having both a wire bonding pad and a contact bonding portion in the same substrate can be manufactured at the same time by a single electrolytic gold plating, which is cost effective. It is advantageous. In memory cards, etc., there are wire bonding pads at the chip connection part, and when the contact bonding part is also in one package, it is not necessary to separately produce hard gold plating and pure gold plating. Sex is very good. Therefore, another aspect of the present invention provides both wire bonding pads and contact joints in the same substrate manufactured by performing one electrolytic gold plating at the same time using the electrolytic gold plating solution of the present invention. It relates to the electronic component that it has.
本発明の電解金めっき液を用いることによって、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品であって、該ワイヤーボンディングパッドと該コンタクト接合部が、同一の金純度で同一のビッカース硬度を有する金皮膜が施されている電子部品が初めて得られるようになった。 By using the electrolytic gold plating solution of the present invention, an electronic component having both a wire bonding pad and a contact joint in the same substrate, the wire bonding pad and the contact joint having the same gold purity and the same An electronic component having a gold film having a Vickers hardness of 1 is obtained for the first time.
すなわち、この場合、該金純度は９９．９質量％以上であり、ワイヤーボンディングパッド用に最適であり、該ビッカース硬度は１００Ｈｖ以上であり、コンタクト接合部用に最適である。 That is, in this case, the gold purity is 99.9% by mass or more, which is optimal for a wire bonding pad, and the Vickers hardness is 100 Hv or more, which is optimal for a contact bonding portion.
以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。また、電解めっき液の組成中の濃度の数値は、その成分が結晶水を含むものである場合は、結晶水を入れない質量から求めた濃度の数値である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist. Moreover, the numerical value of the density | concentration in the composition of an electroplating liquid is a numerical value of the density | concentration calculated | required from the mass which does not put crystallization water, when the component contains crystallization water.
＜金めっき液の調製＞
実施例１〜実施例９、比較例１〜比較例２
シアン化金カリウムを金換算で１０ｇ／Ｌ、表１に示す各実施例及び各比較例に記載の式（１）で示されるアミン化合物を５０ｇ／Ｌ、式（２）で示されるスルホン酸又はその塩を５０ｇ／Ｌ、式（３）で示される複素環式化合物を５ｇ／Ｌとなるように溶解し、ｐＨを５．０に調製して、電解金めっき液とした。なお、ｐＨは２０質量％ＫＯＨ（水酸化カリウム水溶液）と２０質量％硝酸にて５．０に調整し、以下に記載の評価を行った。なお、電解金めっき液の浴温は６０℃に設定した。
<Preparation of gold plating solution>
Example 1 to Example 9, Comparative Example 1 to Comparative Example 2
10 g / L of gold gold cyanide in terms of gold, 50 g / L of the amine compound represented by the formula (1) described in each example and each comparative example shown in Table 1, and the sulfonic acid represented by the formula (2) or The salt was dissolved at 50 g / L and the heterocyclic compound represented by the formula (3) was dissolved at 5 g / L, and the pH was adjusted to 5.0 to obtain an electrolytic gold plating solution. In addition, pH was adjusted to 5.0 with 20 mass% KOH (potassium hydroxide aqueous solution) and 20 mass% nitric acid, and the following evaluation was performed. The bath temperature of the electrolytic gold plating solution was set to 60 ° C.
＜金コバルト合金めっき液の調製＞
比較例３
表１、比較例３に示すように、金コバルト合金めっき液として、シアン化金（Ｉ）カリウム金換算で１０ｇ／Ｌ、硫酸コバルトをコバルト換算で０．３ｇ／Ｌ、クエン酸３カリウム１００ｇ／Ｌ、ピリジン−３−スルホン酸５ｇ／Ｌを含有し、クエン酸でｐＨ４．２に調製し、金コバルト合金めっき液とし、以下の評価を行った。なお、浴温は４０℃に設定した。
<Preparation of gold-cobalt alloy plating solution>
Comparative Example 3
As shown in Table 1 and Comparative Example 3, as a gold-cobalt alloy plating solution, gold (I) cyanide was converted to 10 g / L of potassium gold, cobalt sulfate was converted to 0.3 g / L of cobalt, and tripotassium citrate 100 g / L. L, containing 5 g / L of pyridine-3-sulfonic acid, adjusted to pH 4.2 with citric acid, used as a gold-cobalt alloy plating solution, and evaluated as follows. The bath temperature was set to 40 ° C.
＜金ニッケル合金めっき液の調製＞
比較例４
表１、比較例４に示すように、金ニッケル合金めっき液として、シアン化金（Ｉ）カリウムの形の金１０ｇ／Ｌ、硫酸ニッケルをニッケル換算で０．５ｇ／Ｌ、クエン酸３カリウム１００ｇ／Ｌ、ピリジン−３−スルホン酸５ｇ／Ｌを含有し、クエン酸でｐＨ４．２に調製し、金ニッケル合金めっき液とし、以下の評価を行った。なお、浴温は４０℃に設定した。
<Preparation of gold-nickel alloy plating solution>
Comparative Example 4
As shown in Table 1 and Comparative Example 4, as a gold-nickel alloy plating solution, gold (I) potassium cyanide in the form of gold (10 g / L), nickel sulfate in terms of nickel (0.5 g / L), and tripotassium citrate (100 g) / L, containing 5 g / L of pyridine-3-sulfonic acid, adjusted to pH 4.2 with citric acid, and used as a gold-nickel alloy plating solution, and the following evaluation was performed. The bath temperature was set to 40 ° C.
＜外観の評価方法＞
上記各実施例及び各比較例で調製した金めっき液及び合金めっき液を用いて、表２に示す工程にて、１０ｍｍ×１０ｍｍの銅板上の一次光沢Ｎｉめっき皮膜２．０μｍ上に、金皮膜０．５μｍを生成し、該金皮膜の外観を目視にて確認した。目視により、以下に示す分類を行った。測定結果を表４に示す。
良好 ：全面にレモンイエローの光沢を有する皮膜で、外観良好とする。
ほぼ良好：試験片の一部にくもったような白い無光沢部分があるものの、性能には影響がない皮膜で、外観ほぼ良好とする。
不良 ：ヤケ（赤褐色の無光沢皮膜）が発生、外観不良とする。
<Appearance evaluation method>
Using the gold plating solution and alloy plating solution prepared in each of the above Examples and Comparative Examples, the gold film was formed on the primary bright Ni plating film 2.0 μm on a 10 mm × 10 mm copper plate in the steps shown in Table 2. 0.5 micrometer was produced | generated and the external appearance of this gold film was confirmed visually. The following classification was performed visually. Table 4 shows the measurement results.
Good: A film having a gloss of lemon yellow on the entire surface and good appearance.
Almost good: A film with a white matte portion that looks cloudy on a part of the test piece, but does not affect the performance.
Defect: Burn (reddish-brown matte film) occurs and the appearance is poor.
＜硬度の測定法＞
上記各実施例及び比較例で調製した金めっき液及び合金めっき液を用いて、表３に示す工程にて、１０ｍｍ×１０ｍｍ銅板上に２０μｍの金めっき皮膜を作成し、微小硬度計（ＭＶＫ−Ｇ３ 株式会社アカシ製）を使用し、測定荷重１０ｇで常法によりビッカース硬度を測定した。測定は計５点行い、その平均値を金皮膜の硬度とした。結果を表４に示す。
<Measurement method of hardness>
Using the gold plating solution and alloy plating solution prepared in each of the above Examples and Comparative Examples, a gold plating film of 20 μm was prepared on a 10 mm × 10 mm copper plate in the steps shown in Table 3, and a micro hardness tester (MVK− G3 manufactured by Akashi Co., Ltd.), and Vickers hardness was measured by a conventional method with a measurement load of 10 g. A total of 5 measurements were made, and the average value was taken as the hardness of the gold film. The results are shown in Table 4.
＜電流効率の測定法＞
上記各実施例及び各比較例で調製した金めっき液及び合金めっき液の建浴直後の電流効率を測定した後、銅板を用いてダミー電解処理において、金１ｇ／Ｌ消費させ、金１ｇ／Ｌを補充する操作を計２０回行い、再び電流効率を測定した。これらの結果を表４に示す。なお、電流効率は表３に示す工程によって、１０ｍｍ×１０ｍｍの銅板上に２０μｍの金めっき皮膜を生成する際、クーロンメーター（ＨＦ−２０１ 北斗電工株式会社製）を使用して重量法により測定した。
<Measurement method of current efficiency>
After measuring the current efficiency of the gold plating solution and alloy plating solution prepared in each of the above Examples and Comparative Examples immediately after the bathing, 1 g / L of gold was consumed in a dummy electrolytic treatment using a copper plate. The operation of replenishing was performed 20 times in total, and the current efficiency was measured again. These results are shown in Table 4. The current efficiency was measured by a gravimetric method using a coulomb meter (HF-201, manufactured by Hokuto Denko Co., Ltd.) when a 20 μm gold plating film was formed on a 10 mm × 10 mm copper plate by the steps shown in Table 3. .
＜接触抵抗の測定法＞
上記各実施例及び各比較例で調製した金めっき液及び合金めっき液を用いて、表２に示す工程にて、１０ｍｍ×１０ｍｍの銅板上に光沢Ｎｉめっき皮膜２．０μｍ上の金めっき皮膜０．５μｍを生成し、ヒートプレートにて２６０℃、５分間の熱履歴を加えたもの（熱処理後）及び熱処理前の両方の金皮膜を試料とした。これらの試料を、電気接点シュミレーター（ＣＲＳ−１１３−Ａｕ型 株式会社山崎精機研究所製）を用いて、接触荷重２ｇ、印加電圧２０ｍＶ、印加電流１０ｍＡの条件で、純金製プローブによる４端子法によって接触抵抗の測定を行った。結果を表４に示す。
<Measurement method of contact resistance>
Using the gold plating solution and alloy plating solution prepared in each of the above Examples and Comparative Examples, the gold plating film 0 on the bright Ni plating film 2.0 μm on the 10 mm × 10 mm copper plate in the process shown in Table 2 Samples were prepared by producing 5 μm and adding a heat history at 260 ° C. for 5 minutes on the heat plate (after heat treatment) and before the heat treatment. These samples were subjected to a four-terminal method using a pure gold probe under the conditions of a contact load of 2 g, an applied voltage of 20 mV, and an applied current of 10 mA using an electric contact simulator (CRS-113-Au type, manufactured by Yamazaki Seiki Laboratories). The contact resistance was measured. The results are shown in Table 4.
＜析出皮膜純度の測定法＞
上記各実施例及び各比較例で調製した金めっき液及び合金めっき液を用いて、表３に示す工程にて、３５ｍｍ×３５ｍｍの銅板上に２０μｍの金めっき皮膜を生成し、硝酸にて銅素材を溶解して金箔を作成した。作成した金箔の重量を測ったのち、金箔を王水２０ｍＬにて溶解させ、ＩＣＰ発光分光分析装置（ＳＰＳ３０００ セイコーインスツルメンツ株式会社製）にて不純物元素としてＣｕ、Ｎｉ、Ｃｏ、Ｆｅ、Ｋ、Ｎａの定量分析を行い、析出金重量と不純物重量から金純度を算出した。結果を表４に示す。
<Measurement method of deposited film purity>
Using the gold plating solution and alloy plating solution prepared in each of the above Examples and Comparative Examples, a 20 μm gold plating film was formed on a 35 mm × 35 mm copper plate in the steps shown in Table 3, and copper was added with nitric acid. The material was melted to create a gold leaf. After measuring the weight of the prepared gold foil, the gold foil was dissolved in 20 mL of aqua regia, and Cu, Ni, Co, Fe, K, Na were used as impurity elements with an ICP emission spectroscopic analyzer (SPS3000 manufactured by Seiko Instruments Inc.). Quantitative analysis was performed, and gold purity was calculated from the weight of precipitated gold and the weight of impurities. The results are shown in Table 4.
＜ワイヤーボンディングプル強度の測定方法＞
上記各実施例及び各比較例で調製した金めっき液及び合金めっき液を用いて、表３に示す工程にて、１０ｍｍ×１０ｍｍのガラスエポキシ上銅張り板上に光沢Ｎｉめっき皮膜２．０μｍ上の金めっき皮膜０．５μｍを生成し、エタノールに浸漬して前処理した後、ウェッジ‐ウェッジ型ボンダー（ＷＥＳＴ ＢＯＮＤ ５４００−４５Ｇ ＷＥＳＴ ＢＯＮＤ社製）を使用して、金ワイヤー径２５μｍφ、荷重８０ｇ、超音波 ８００ｍＷ １００ｍｓｅｃ、温度１５０℃の条件で、ワイヤーボンディングを行ったのち、ワイヤーボンディングされた金ワイヤーのプル強度の測定を行った。また、測定は計２０回行い、平均プル強度８ｇ以上を優れたものとした。結果を表４に示す。
<Measurement method of wire bonding pull strength>
Using the gold plating solution and the alloy plating solution prepared in each of the above examples and comparative examples, a bright Ni plating film on a 10 mm × 10 mm glass-epoxy copper-clad plate on the surface of 2.0 μm in the process shown in Table 3 A gold plating film of 0.5 μm was produced, pretreated by immersing in ethanol, and then using a wedge-wedge type bonder (manufactured by WEST BOND 5400-45G WEST BOND), a gold wire diameter of 25 μmφ, a load of 80 g, After performing wire bonding under the conditions of ultrasonic wave 800 mW 100 msec and temperature 150 ° C., the pull strength of the wire wire bonded was measured. Moreover, the measurement was performed 20 times in total and the average pull strength was 8 g or more. The results are shown in Table 4.
表４より、本発明の電解金めっき液を使用した実施例１〜実施例９は、金皮膜外観が良好又はほぼ良好で、硬度が１００Ｈｖを大きく上回り、ダミー電解後の析出効率が建浴直後の析出効率とほとんど変化しないことが分かった。また、熱処理後においても接触抵抗値の上昇がなく、ワイヤーボンディングプル強度も良好であった。 From Table 4, Examples 1 to 9 using the electrolytic gold plating solution of the present invention have good or almost good gold film appearance, the hardness greatly exceeds 100 Hv, and the deposition efficiency after dummy electrolysis is immediately after the bathing It was found that there was almost no change with the deposition efficiency of. Further, the contact resistance value did not increase even after the heat treatment, and the wire bonding pull strength was good.
これに対し、比較例１は、金めっき皮膜外観は良好で硬度も１００Ｈｖを大きく上回ったが、ダミー電解後の電流効率が建浴直後の電流効率と比較して、約３０％も低下してしまった。また、比較例２は金皮膜外観と硬度の２点の測定結果が不良であった。比較例３及び比較例４では、熱処理後の接触抵抗値が上昇しており、また、ワイヤーボンディングプル強度も低い値となった。 In contrast, in Comparative Example 1, the appearance of the gold plating film was good and the hardness greatly exceeded 100 Hv, but the current efficiency after dummy electrolysis was reduced by about 30% compared to the current efficiency immediately after the bathing. Oops. In Comparative Example 2, the measurement results of the gold film appearance and hardness were poor. In Comparative Example 3 and Comparative Example 4, the contact resistance value after the heat treatment was increased, and the wire bonding pull strength was also low.
本発明の電解金めっき液は、金めっき皮膜の外観に優れ、ビッカース硬度も１００Ｈｖを大きく上回って硬質でありながら、硬質金めっきと呼ばれる金合金めっきの弱点であった加熱処理による接触抵抗の上昇の問題及び、ワイヤーボンディング特性を解決することができた。本発明の電解金めっき液を用いれば、同時に１回の電解金めっきを行うことによって、同一基板内にワイヤーボンディングパッドとコンタクト接合部の両方を有する電子部品が製造される。 The electrolytic gold plating solution of the present invention is excellent in the appearance of a gold plating film, and has a Vickers hardness greatly exceeding 100 Hv and is hard, but the contact resistance is increased by heat treatment, which is a weak point of gold alloy plating called hard gold plating. Problem and wire bonding characteristics could be solved. When the electrolytic gold plating solution of the present invention is used, an electronic component having both a wire bonding pad and a contact bonding portion in the same substrate is manufactured by performing electrolytic gold plating once at the same time.
本発明の電解金めっき液は、金めっき皮膜外観に優れ、硬質であり、加熱処理による接触抵抗の上昇を抑え、ワイヤーボンディング特性を向上させるので、電子部品の現在一般に実用化されている電解ニッケル／金めっき分野等に広く利用されるものである。更に、電解金めっき液としてもランニングによる析出効率の低下が少ないことから建浴回数を大幅に減らすことが可能で経済的である。 The electrolytic gold plating solution of the present invention has an excellent gold plating film appearance, is hard, suppresses an increase in contact resistance due to heat treatment, and improves wire bonding characteristics. / Widely used in the field of gold plating. Furthermore, since the electrolytic gold plating solution is less likely to decrease the deposition efficiency due to running, it is economical because the number of times of bathing can be greatly reduced.
Claims (16)
Ｈ２Ｎ−（Ｒ１−ＮＨ）ｎ−Ｈ （１）
［式（１）中、Ｒ１は置換基を有していてもよい炭素数１〜１２の、アルキレン基、アリーレン基若しくはアルキレンアリーレン基を示し、ｎは１以上の自然数である。］
H 2 N- (R 1 -NH) n -H (1)
[In Formula (1), R 1 represents an alkylene group, an arylene group or an alkylene arylene group having 1 to 12 carbon atoms which may have a substituent, and n is a natural number of 1 or more. ]
ＨａＮ−（ＳＯ３Ｘ）ｂ （２）
［式（２）中、ｘはＨ、Ｎａ、Ｋ又はＮＨ４を示し、ａは０、１又は２であり、ｂは１、２又は３であり、ａ＋ｂ＝３である。］ Furthermore, the electrolytic gold plating solution of Claim 1 containing the sulfonic acid or its salt shown by following formula (2).
H a N- (SO 3 X) b (2)
[In the formula (2), x represents H, Na, K or NH 4 , a is 0, 1 or 2, b is 1, 2 or 3, and a + b = 3. ]
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