SG181529A1 - Electrolytic hard gold plating solution and plating method using same - Google Patents
Electrolytic hard gold plating solution and plating method using same Download PDFInfo
- Publication number
- SG181529A1 SG181529A1 SG2012041463A SG2012041463A SG181529A1 SG 181529 A1 SG181529 A1 SG 181529A1 SG 2012041463 A SG2012041463 A SG 2012041463A SG 2012041463 A SG2012041463 A SG 2012041463A SG 181529 A1 SG181529 A1 SG 181529A1
- Authority
- SG
- Singapore
- Prior art keywords
- gold
- plating solution
- salt
- plating
- electrolytic hard
- Prior art date
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- 239000010931 gold Substances 0.000 title claims abstract description 116
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 115
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000007747 plating Methods 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- -1 aromatic sulfonic acid compound Chemical class 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- 239000000243 solution Substances 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 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
- 235000011082 potassium citrates Nutrition 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 description 1
- GWGBNENHEGYJSN-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GWGBNENHEGYJSN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- ODHCTXKNWHHXJC-UHFFFAOYSA-N 5-oxoproline Chemical compound OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 description 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229960000458 allantoin Drugs 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- LJJNEPKMBSUEND-UHFFFAOYSA-O azanium;gold;cyanide Chemical compound [NH4+].[Au].N#[C-] LJJNEPKMBSUEND-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 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
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- LONQOCRNVIZRSA-UHFFFAOYSA-L nickel(2+);sulfite Chemical compound [Ni+2].[O-]S([O-])=O LONQOCRNVIZRSA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229940093928 potassium nitrate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 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 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
AbstractDisclosed is a plating solution which does not generate pinholes in a gold film even if the gold film has a thickness5 of less than 0.1µm. Partial plating is performed using an electrolytic hard gold plating solution containing gold cyanide and/or gold cyanide salt, water-soluble cobalt salt or water-soluble nickel salt, an electric conductive salt of organic acid, an aromatic sulfonic acid compound, a10 combination of one or more items selected from group consisting of carboxylic acids, oxycarboxylic acids, and the salts thereof, and a nitrogen-containing five-membered heterocyclic compound. Consequently, pinholes are not• generated in a gold film even if the gold film has a15 thickness of less than 0.1pm.
Description
ELECTROLYTIC HARD GOLD PLATING SOLUTION AND PLATING
METHOD USING SAME
[0001]
The present invention relates to an electrolytic hard gold plating solution capable of forming a plating film which hardly generates pinholes even when formed in a thin film and which is dense, as well as to a plating method using the plating solution. The present invention relates particularly to an electrolytic hard gold plating solution preferably used for selective plating of electronic parts such as connector and the like, as well as te a plating method using the plating solution.
[0002]
Owing to the recent progress of IT, electronic apparatuses such as mobile phone, note type personal computer and the like have rapidly come to possess a lighter weight, a smalier size and a higher performance. In connection therewith, needs for smaller size and higher reliability have become stronger for electronic parts constituting the above- mentioned electronic apparatuses. Gold plating is in wide use in the electronic parts constituting the above-mentioned electronic apparatuses.
[0003]
For example, hard gold plating superior in abrasion resistance is applied to a contact member which becomes an electric contact of a connector electrically connecting electronic apparatuses or electronic parts.
[0004]
Contact member for electronic parts is produced generally by the following method. First, nickel plating is applied on a base material (e.g. copper material), whereby a nickel film is formed. Next, hard geld plating is applied on the nickel film, whereby a gold film is formed. In this way, there is obtained a contact member in which a nickel film and a gold film have been formed on a copper material in this order. | Co oo
[0005]
Since gold is expensive, gold film is made thin for gold saving. However, when a gold film is formed using a conventional gold plating solution, a large number of pinholes appears therein when the gold film has a thickness of 0.1 pum or smaller. When pinholes are present in a gold film, the nickel film (which is a lower film} undergoes air oxidation via the pinholes, generating nickel oxide. This nickel oxide gives rise to, for example, an increase in electric resistance at contact point, causing a change in electric properties of electronic apparatus. As a result, the electronic apparatus comes to have inconveniences. : [0006]
Thus, a gold film having a large number of pinholes therein has no sufficient protectability for nickel film.
Accordingly, it is desired that the gold film has no pinhole.
[0007]
In. Patent Literature 1, 1t is described that selective plating is applied to a contact member using a hard gold plating solution containing a lustering agent. This plating solution enables uniform electrodeposition. With this plating solution, however, the lustering agent component is taken into the gold film formed. When the additive component such as lustering agent component or the like is taken into the gold film, the gold purity of the gold film is reduced.
As a result, the contact member comes to have an increased contact resistance or have a reduced corrosion resistance. : Citation List
Patent Literature
[0008] : PTL 1: Patent No. 3933930 : Summary of Invention
[0009]
A task to be achieved by the present invention is to provide an electrolytic hard gold plating sclution which is preferably used in selective plating, etc. and which gives no pinhole in the gold film formed even when the film has a thickness of 0.1 pm or smaller.
[0010]
Other task to be achieved by the present invention is to provide a plating method using such an electrolytic hard .
gold plating sclution.
Solution to Problem 100113
In order to achieve the above task, the present inventors made an investigation first on selective plating.
As a result, it was found that, when an organic oxidizing agent is compounded in a plating solution, deposition of gold can be suppressed uniquely in a low current density range, and a patent application was made on this finding (Japanese patent Application 2009-165730). This organic oxidizing agent raises the oxidation and reduction potential of gold uniquely in a low current density range {a current density of : 20 A/dm? or lower) and suppresses gold deposition. Meanwhile, . : 15 the organic oxidizing agent does not suppress gold deposition : in a medium to high current density range (a current density of 20 to 200 A/dm?). Thus, the area in which a plating film is fermed, can be contrclled by contrelling the current density employed. For the above reason, an electrolytic hard gold plating solution containing an organic oxidizing agent can be preferably used in selective plating.
[0012]
Next, the present inventors made an investigation on thin-film formation of gold film. As a result, it was found that, when the above-mentioned plating solution contains an organic crystal-controlling agent of the present invention, the gold film formed therewith generates no pinhole even when the gold film formed has a thickness of about 0.05 pm. The present inventors further found that the above-mentioned plating solution can form a gold film of high gold purity.
The present inventors completed the present invention based : on the above findings. ; [0013] : :
The present invention which has achieved the above task, is as described below.
[0014]
[1] An electrolytic hard gold plating solution comprising at least one member of a gold cyanide and a gold - 10 cyanide salt, : : a water-soluble cobalt salt or a water-soluble nickel salt, an electric conductive salt of organic acid, an aromatic sulfonic acid compound, at least one member selected from the group consisting of a carboxylic acid, an oxycarboxylic acid, and salts thereof, and a hitrogen-containing five-membered heterocyclic : compound. :
[0015]
[2] The electrolytic hard gold plating solution according to [1], wherein the concentration of the nitrogen-containing five-membered heterocyclic compound is 1 ~ 5C g/L.
[0016]
[3] The electrolytic hard gold plating solution according to [1], wherein the pH of the plating solution is in a range of 3 to 7.
[0017]
[4] A plating method which comprises spraying the electrolytic hard gold plating sclution cf [1] onto a to-be- plated area of a to-be-plated material to form a gold film on the to-be-plated area.
[0018]
The gold film formed with the electrolytic hard gold plating solution of the present inventicn generates no ~~ pinhole even when the £1lm has a thickness of about 0.05 pm. 16 The nickel film beneath the gold film is c¢ompletely covered : : and protected by the gold film and, therefore, the material plated with the present plating solution has high corrosion resistance. Further, with the present electrolytic hard geld : plating solution, the use amount of gold can be made small, resulting in superior economy. oo Description of Embodiments -
[0019] {(Flectrolytic hard gold plating solution)
In-depth description is made below con the electrolytic hard geld plating solution of the present invention.
[0020]
In the electrolytic hard gold plating solution of the present invention, at least either of a gold cyanide and a gold cyanide salt is compounded as a source of gold. Both of them may be compounded. As the gold cyanide salt, there are mentioned, for example, gold potassium cyanide, gold sodium cyanide and gold ammonium cyanide. They may be compounded singly or in two or more kinds.
[0021] }
In the present electrolytic hard geld plating solution, the concentration of the gold cyanide and the gold cyanide
CL salt 1s 0.1 to 20 g/bL, preferably 2 to 15 g/L, particularly preferably 3 to 10 g/L in terms of total gold concentration.
With a gold concentration of lower than 0.1 g/L, the cathode current efficiency is low, making it impossible to obtain a gold film of intended thickness. With a gold concentration higher than 20 g/L, the cathode current efficiency does not } increase in proportion to the gold concentration and there is oo 10 nc advantage cf using a high .gold concentration; further, the a drag out of plating solution in plating operation is large, resulting in large waste of plating solution. © 10022] oo
In the present electrolytic hard gold plating sclution, an aromatic sulfonic acid compound is compounded. The aromatic sulfonic acid compound acts as an organic oxidizing agent. As the aromatic sulfonic acid compound, there are mentioned, for example, 2-nitrobenzenesul fonic acid, 3- } nitrobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 2,4- dinitrobenzenesulfonic acid, Z2-aminobenzenesulfonic acid, 3- aminobenzenesufonic acid, 4-aminobenzenesulfonic acid, and salts thereof. Of these, an aromatic sulfonic acid compound having nitro group as a substituent is preferred. They may be compounded singly or in two or more kinds.
[0023]
The electrolytic hard gold plating solution containing such an arcmatic sulfonic acid compound raises the oxidation reduction potential of gold uniquely in a low current density range (a current density of lower than 20 A/dm’). As a result, gold deposition is suppressed in a low current density range. Meanwhile, the electrolytic hard gold plating solution containing such an aromatic sulfonic acid compound does not suppress gold deposition in a medium to high current density range (a current density of 20 to 200 A/dm?) . As a © result, a normal gold film is formed in a medium to high current density range.
[0024] .
With the electrolytic hard gold plating solution of the present invention, formation of plating film can be suppressed at an area of to-be-plated material other than the to-be-plated area thereof, by controlling the current density employed.
[0025]
The concentration of the organic oxidizing agent compounded in the present electrolytic hard gold plating solution is 0.1 to 20 g/L, preferably 0.5 to 5 g/L, particularly preferably 1 to 3 g/L. With a concentration of organic oxidizing agent of lower than 0.1 g/L, the effect of suppression of gold deposition in a low current density range oo is small. With a concentration of organic oxidizing agent of higher than 20 g/L, the effect of suppression of gold deposition in a low current density range 1s unchanged and high.
[0026] -
In the present electrolytic hard gold plating solution, a carboxylic acid or an oxycarboxylic acid or a salt thereof is compounded. They act as a complexing agent. As the carboxylic acid, the oxycarboxylic acid or the salt thereof,
there are mentioned, for example, formic acid, glycolic acid, lactic acid, oxybenzoic acid, succinic acid, malonic acid, . malic acid, tartaric acid, phthalic acid, diglycolic acid, : citric acid, and salts thereof. As the salt, there are preferred alkali metal salts such as sodium salt, potassium salt and the like; alkaline earth metal salts such as calcium salt and the like; and salts of ammonia, amine, etc. They may be - compounded singly cr in two or more kinds.
[0027]
In the present electrolytic hard gold plating sclution, - the concentration of complexing agent is 1 to 100 g/L, preferably 5 to 600 g/L. With a concentration of complexing agent of lower than 1 g/L, the inorganic impurities : dissolving out from the plated material tend to be taken into the gold film formed. The inorganic impurities taken into the gold film reduce the gold purity of the gold film. As a result, the gold film has inferier appearance, and the contact member has an increased contact resistance and has lower corrosion resistance. With a concentration of complexing agent of higher than 100 g/L, no effect corresponding to such a high concentration is obtained, and such a concentration is nct economical.
[6028]
In the present electrolytic hard gold plating solution, a water-soluble cobalt salt or a water-soluble nickel salt is compounded. As the cobalt salt, there are mentioned, for example, cobalt sulfate, cobalt nitrate, cobalt chloride, and basic cobalt carbonate. As the nickel salt, there are mentioned, for example, nickel sulfate, nickel sulfamate,
nickel sulfite, and nickel chloride. They may be compounded singly or in two or more kinds. : . [0029]
In the present electrolytic hard gold plating solution, the concentration of cobalt salt or nickel salt is 0.01 to 10 g/L, preferably 0.1 to 1.0 g/L. With a concentration of cobalt salt or nickel salt of lower than 0.01 g/L, the gold film formed has a low hardness. With a concentration of cobalt salt or nickel salt of higher than 1C g/L, no effect corresponding to such a high concentration is obtained, and such a concentration is not economical. By compounding the cobalt salt or the nickel salt in the above concentration, oo the gold film formed has a hardness of 150 to 200 HV.
Incidentally, “water-soluble” of the cobalt salt or the nickel salt, compounded in the present electrolytic hard gold plating solution refers to such a water solubility that the oo salt can be dissolved in water in the above-menticned
N concentration.
[0030] - In the present electrolytic hard gold plating solution, . an electric conductive salt of organic acid is compounded. : As the electric conductive salt of organic acid, there are mentioned, for example, potassium formate, potassium citrate, potassium phosphate, potassium nitrate, and potassium succinate. They may be compounded singly or in two or more oo kinds.
[0031]
In the present electrolytic hard gold plating solution, the concentration of electric conductive salt of organic acid is 10 to 200 g/L, preferably 50 to 100 g/L. With a concentration of electric conductive salt of organic acid of lower than 10 g/L, the gold film formed has inferior appearance and no normal gold film is obtained. With a concentration of electric conductive salt of organic acid of higher than 200 g/L, no effect corresponding to such a high concentration is obtained, and such a concentration is not economical.
[0032]
EY | In the present electrolytic hard gold plating solution, a nitrogen-containing five-membered heterocyclic compound is compounded. The nitrogen-containing five-membered } heterocyclic compound acts as an organic crystal-controlling agent. The present inventor considers as follows. The nitrogen-containing five-membered heterocyclic compound 1s adsorbed on the gold cyanide ion present in the plating bath, or is adsorbed or forms a complex with the gold ion after ligand disengagement (cyanide ion), in an electric double layer, whereby the growth of gold crystal is controlled and a dense gold film is formed. The nitrogen-containing five- membered heterocyclic compound used in the present invention is not taken into the gold film formed; therefore, the gold film has a high gold purity.
[0033]
As the nitrogen-containing five-membered heterocyclic : compound, there are mentioned, for example, imidazole, 2- methylimidazole, pyrazole, 3,5-dimethyloyrazole, 2- imidazoline, 2-pyrrolidone, hydantoin, 5, 5-dimethylhydantoin, allantoin, succinic acid imide, DL-pyroglutamic acid, and salt thereof.
[0034] : Tn the present electrolytic hard gold plating solution, the concentration of nitrogen-containing five-membered "5 heterocyclic compound is 1 to 50 g/L, preferably 5 to 20 g/L, particularly preferably 8 te 12 g/L. With 2 concentration of nitrogen-containing five-membered heterocyclic compound of lower than 1 g/L, the effect of crystal controlling is small and no dense gold film is obtained. With a concentration of nitrogen-containing five-membered heterocyclic compound of oo higher than 50 g/L, no effect corresponding to such a high concentration is obtained, and such a concentration is not economical .
[0035]
The present electrolytic hard gold plating soluticn is usable in a pH range of 3.0 to 7.0, and is used preferably in : a pH range of 4.0 to 5.0. When the pH is lower than 4.0, the oo cathode current efficiency is low, making it difficult to ‘obtain a gold film having an intended thickness. Meanwhile, when the pH is higher than 5.0, the gold film formed has a redd: sh appearance, making it difficult to obtain a normal gold film. Incidentally, as the pH-adjusting agent, there are mentioned, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide and dilute sulfuric acid. [C036]
The present electrolytic hard gold plating solution may - ‘contain other substances as long as the effect of the present invention is not impaired thereby.
[0037] oo
The plating with the present electrolytic hard gold plating solution can be conducted by a known plating method.
The plating can also be conducted by a selective plating method of using a platinum-made nozzle as an anode and a to-
Dbe-plated material as a cathode and spraying the present electrolytic hard gold plating solution from the platinum- made nozzle onte the to-be-plated material.
Examples oo : 10 [0038] :
The constitution of the test equipment used and the evaluation method used are as follows.
[0039]
A copper plate of 32 mm x 150 mm x 0.2 mm was prepared.
On this copper plate was formed a nickel film in a thickness of 2 pm, using a nickel sulfamate plating solution, and the resulting plate was used as a sample. On this sample was superimposed 2 silicon rubber-made masking plate having a : square opening of 10 mm x 10 mm, and they were fixed.
[0040]
A plating sclution was sent to the injection orifice of plating sclution using a pump. The plating solution was injected from the injection orifice onto the opening of the masking plate. Thereby, selective plating was conducted on the sample. A platinum nozzle of &§ mm in diameter was fitted to the injection orifice of plating solution, and this nozzle was used as an anode. oo [0041]
The measurement of the thickness of the gold film oo formed was conducted using a fluorescent X-ray film thickness
Co © tester SEA 5120 manufactured by SII.
[0042] - The pinholes generated in the gold film were evaluated by the test method by exposure to nitric acid vapor (JIS H : 8620 10.5) which is a porosity test described in Japanese
N Industrial Standards (JIS). In the porosity test, the sizes
E and numbers of pinholes in plating layer are measured. In oo : the test by exposure to nitric acid vapor, the above sample oo 10 after selective plating is placed on a ceramic plate put in a desiccator containing nitric acid at the bottom and is allowed to stand for 1 hour at about 23°C. The nitric acid } vapor generated in the desiccator passes through the pinholes .. . of sample and corrodes the nickel film of sample. When the nickel film (under layer) is corroded, spots appear on the gold film. The condition of spots was examined referring to the rating number standard chart specified in Method of corrosion resistance test (JIS H 8502 11.53).
[0043] (Example 1)
Potassium cyanide: 5 g/L (as Au)
Potassium citrate: 70 g/L © Citric acid: 50 g/L
Potassium formate: 20 g/L
Cobalt sulfate: 0.96 g/L 2-Nitrobenzenesulfonic acid: 2 g/L
Imidazole: 10 g/L
[0044]
A plating solution was prepared using the above ~ composition. The plating solution was adjusted to a pH of
ST
- 4.2, and selective plating was conducted on a sample at a ] solution temperature of 55°C and at a current density of 40
A/dm’ so as to give a gold film thickness of 0.05 um. The - © gold film formed on the sample had a lemon yellow color and uniform and good appearance. With respect to the corrosion test, the rating number was 9.5-5 and the total corroded area ratio was above 0.02% but 0.05% or below.
[0045] (Examples 2 to 5) (Comparative Examples 1 to 2)
Each plating solution was prepared according to the 100 formulation shown in Table 1 and, using the solution, © selective plating was conducted on each sample in the same . manner as in Example 1. The gold film formed on each sample had a lemon vellow color and uniform and good appearance. . | The results of corrosion test are shown in Table 2.
[0046]
Lo . o|lolo ™
Soe || ey Slo
O Ef : .
Oo, 1 gle |o|oo Nin lo
S x =| ey A bp | = 0 ol|lo|lo N . “ © wo . <f : olo|o ™N ) . I. Oo no m — o|lo|lo oN . Ln oN |= Lo 3 CFE | EEE . [] 0 fis
I
~ bo. lolo|o © oN 2 | | <t ’ ba : ol|lo|o oN . “ o wo 0 co = ol |o O al |o 2 Ww Q - iT I] — 1 oP HE . oH sEl0|O = OQ © S 2 > b Slee nn |9 ce = S15
Q o 0, —
EB =e Ol @| © QO Po oO GT = )
OT |(Yd | 4H | HAH « -H WH QO og Q o 2 a [cd 0 alo |e Q i oo ~~ s|lo|lg]l =z ™ Id aH g 0 sola cae” 5 gs n|l—|- — o . - - Q : Jalal ofall] & |g 828 2 1S Eas ol o|-+|o]A|e OQ 0 Olas 2 + DF oT MH mo] | MOTH NIT > ® = MD . —H nleie|elalo Pp -Alg alamo gl |= OEY ~ o w|lol=|ololal ole olgli| ~Alzlo ds } 0 —|ujom]ulzle 2 © QlH(N (0 T| ow ~0 ~~ oon Lo on = PI . wg 59
I op 0 — oo m+ gq FE ~ | Odd PC -H
OP OS Od T O oo — BE ~~ a 5iu88e i 0 0
[0047]
Table 2
Rating number Total corroded area ratio %
Above 0.02% but 0.05% or below
Above 0.05% but 0.07% or below
Ex. 3 | 9.5-6 | Above 0.02% but 0.05% or below
Above 0.02% but 0.05% or below
Above 0.05% but 0.07% or below : Comp. | 4-1 | Above 2.50% but 5.00% or below
Ex. 1 | | a
Comp. 4-4 Above 2.50% but 5.00% or below
Ex. 2 ‘5s [0048]
In Examples 1 to 5, corrosion was significantly suppressed as compared with Comparative Examples 1 to 2.
[0049]
As 1s clear from above, the electrolytic hard gold plating solution of the present invention can form a gold film which is extremely few in pinholes even when the film has a thickness of 0.1 pm or smaller and which is dense. As a result, the material plated with the present plating solution is superior in corrosion resistance.
Claims (4)
- : CLAIMS[Claim 1] An electrolytic hard gold plating solution comprising : at least one member of a gold cyanide and a gold cyanide salt, a water-scluble cobalt salt or a water-soluble nickel salt, an eclectric conductive salt of organic acid, an aromatic sulfonic acid compound, . 10 at least one member selected from the group consisting : of a carboxylic acid, an oxycarboxylic acid, and salts - thereof, and : =! nitrogen—-containing five-membered heterccyclic compound.
- [Claim 2] oo : The electrolytic hard geld plating solution according : to Claim 1, wherein the concentration of the nitrogen-—©. containing five-membered heterocyclic compound is 1 ~ 50 g/L.
- [Claim 3] oo SE ) The electrolytic hard gold plating solution according © to Claim 1, wherein the pH of the plating solution is in a range of 3 to 7.
- [Claim 4] . A plating method which comprises spraying the +25 electrolytic hard gold plating solution of Claim 1 onto a to- C be-plated area of a to-be-plated material to form a gold film .on the to-be-plated area.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009279409A JP2011122192A (en) | 2009-12-09 | 2009-12-09 | Electrolytic hard gold plating liquid and plating method using the same |
| PCT/JP2010/071304 WO2011070933A1 (en) | 2009-12-09 | 2010-11-30 | Electrolytic hard gold plating solution and plating method using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SG181529A1 true SG181529A1 (en) | 2012-07-30 |
Family
ID=44145478
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|---|---|---|---|
| SG2012041463A SG181529A1 (en) | 2009-12-09 | 2010-11-30 | Electrolytic hard gold plating solution and plating method using same |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2511400A4 (en) |
| JP (1) | JP2011122192A (en) |
| KR (1) | KR20120120134A (en) |
| CN (1) | CN102695819A (en) |
| SG (1) | SG181529A1 (en) |
| TW (1) | TW201137184A (en) |
| WO (1) | WO2011070933A1 (en) |
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| JP5025815B1 (en) * | 2011-08-10 | 2012-09-12 | 小島化学薬品株式会社 | Hard gold plating solution |
| JP5758361B2 (en) * | 2012-08-31 | 2015-08-05 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Non-cyanide gold-palladium alloy plating solution and plating method |
| JP5152943B1 (en) * | 2012-09-19 | 2013-02-27 | 小島化学薬品株式会社 | Method for producing low free cyanogen gold salt |
| JP7219120B2 (en) * | 2019-03-04 | 2023-02-07 | Ｅｅｊａ株式会社 | Electrolytic gold plating solution and its manufacturing method, gold plating method and gold complex |
| CN117542818B (en) * | 2024-01-10 | 2024-04-05 | 深圳市联合蓝海应用材料科技股份有限公司 | Gold-silver alloy bump and preparation method and application thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2355581C3 (en) * | 1973-11-07 | 1979-07-12 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Galvanic bright gold bath with high deposition rate |
| GB8501245D0 (en) * | 1985-01-18 | 1985-02-20 | Engelhard Corp | Gold electroplating bath |
| JPS637390A (en) * | 1986-06-26 | 1988-01-13 | Nippon Engeruharudo Kk | Gold-cobalt alloy plating liquid |
| CN1205360C (en) * | 1999-06-17 | 2005-06-08 | 德古萨电解技术有限公司 | Acid bath for galvanic deposition of shining gold and gold alloy layers and brightener therefor |
| FR2828889B1 (en) * | 2001-08-24 | 2004-05-07 | Engelhard Clal Sas | ELECTROLYTIC BATH FOR THE ELECTROCHEMICAL DEPOSITION OF GOLD AND ITS ALLOYS |
| US7128822B2 (en) * | 2003-06-04 | 2006-10-31 | Shipley Company, L.L.C. | Leveler compounds |
| JP4320606B2 (en) * | 2004-03-15 | 2009-08-26 | 上村工業株式会社 | Gold plating bath |
| SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
| JP5559455B2 (en) * | 2007-06-29 | 2014-07-23 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film obtained using the same |
| JP2009165730A (en) | 2008-01-18 | 2009-07-30 | Kozo Motoki | Cleaning brush |
| JP5216633B2 (en) * | 2008-03-19 | 2013-06-19 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Method for suppressing background plating |
| CN101550571A (en) * | 2008-03-31 | 2009-10-07 | 恩伊凯慕凯特股份有限公司 | Electroplating solution containing gold for partly electroplating |
| CN102105623B (en) * | 2008-06-11 | 2013-10-02 | 日本高纯度化学株式会社 | Electrolytic gold plating solution and gold film obtained using same |
-
2009
- 2009-12-09 JP JP2009279409A patent/JP2011122192A/en not_active Ceased
-
2010
- 2010-11-30 CN CN2010800528667A patent/CN102695819A/en active Pending
- 2010-11-30 SG SG2012041463A patent/SG181529A1/en unknown
- 2010-11-30 EP EP10835855.7A patent/EP2511400A4/en not_active Withdrawn
- 2010-11-30 KR KR1020127012784A patent/KR20120120134A/en not_active Application Discontinuation
- 2010-11-30 WO PCT/JP2010/071304 patent/WO2011070933A1/en active Application Filing
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| KR20120120134A (en) | 2012-11-01 |
| WO2011070933A1 (en) | 2011-06-16 |
| JP2011122192A (en) | 2011-06-23 |
| CN102695819A (en) | 2012-09-26 |
| TW201137184A (en) | 2011-11-01 |
| EP2511400A1 (en) | 2012-10-17 |
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