EP0343816A1 - Verfahren zur stromlosen Metallabscheidung - Google Patents
Verfahren zur stromlosen Metallabscheidung Download PDFInfo
- Publication number
- EP0343816A1 EP0343816A1 EP89304821A EP89304821A EP0343816A1 EP 0343816 A1 EP0343816 A1 EP 0343816A1 EP 89304821 A EP89304821 A EP 89304821A EP 89304821 A EP89304821 A EP 89304821A EP 0343816 A1 EP0343816 A1 EP 0343816A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- liquor
- alkali metal
- deposition
- potassium
- 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.)
- Withdrawn
Links
- 230000008021 deposition Effects 0.000 title claims abstract description 52
- 239000010931 gold Substances 0.000 claims abstract description 89
- 229910052737 gold Inorganic materials 0.000 claims abstract description 83
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 34
- -1 alkali metal gold cyanide Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002738 chelating agent Substances 0.000 claims abstract description 9
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 claims abstract description 7
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052716 thallium Inorganic materials 0.000 claims description 10
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 7
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 abstract description 2
- 229940119523 thallium sulfate Drugs 0.000 abstract description 2
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract 2
- 238000000151 deposition Methods 0.000 description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000000243 solution Substances 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 21
- 229910052700 potassium Inorganic materials 0.000 description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 16
- 239000011591 potassium Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000007747 plating Methods 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 11
- 230000002269 spontaneous effect Effects 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007306 turnover Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002344 gold compounds Chemical class 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000000337 buffer salt Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance 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
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- TVVRFUOKLKGUKT-UHFFFAOYSA-N 1a,7a-dihydronaphtho[2,3-b]oxirene-2,7-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2C1O2 TVVRFUOKLKGUKT-UHFFFAOYSA-N 0.000 description 1
- ZRXHLJNBNWVNIM-UHFFFAOYSA-N 3-methyl-1-benzofuran Chemical compound C1=CC=C2C(C)=COC2=C1 ZRXHLJNBNWVNIM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 description 1
- ZTQYEZDTWTZXPF-UHFFFAOYSA-N boron;propan-2-amine Chemical compound [B].CC(C)N ZTQYEZDTWTZXPF-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- DXONONHRBADGKK-UHFFFAOYSA-N gold;isoindole-1,3-dione;potassium Chemical compound [K].[Au].C1=CC=C2C(=O)NC(=O)C2=C1 DXONONHRBADGKK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 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
- QMKIMYFCMFAFAH-UHFFFAOYSA-J potassium;gold(3+);5-oxo-3,4-dihydropyrrol-2-olate Chemical compound [K+].[Au+3].[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1 QMKIMYFCMFAFAH-UHFFFAOYSA-J 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- HSSLDCABUXLXKM-UHFFFAOYSA-N resorufin Chemical compound C1=CC(=O)C=C2OC3=CC(O)=CC=C3N=C21 HSSLDCABUXLXKM-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- RONADMZTCCPLEF-UHFFFAOYSA-M tetrazolium violet Chemical compound [Cl-].C1=CC=CC=C1C(N=[N+]1C=2C3=CC=CC=C3C=CC=2)=NN1C1=CC=CC=C1 RONADMZTCCPLEF-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Definitions
- the present invention relates to a liquor for use as an electroless gold deposition bath and to a process for depositing gold on a substrate using such a liquor.
- An electroless (autocatalytic) deposition system has two main advantages over conventional electroplating. It can deposit metal on electrically isolated or non-conducting substrates and it can deposit an even thickness of metal over a component, regardless of geometry. For some time the electronics industry has been searching for a truly autocatalytic gold deposition process. Most of those previously developed have proved unsuitable due to the instability of the solutions. A survey of previously proposed electroless gold deposition systems has been provided by H.O. Ali and I.R.A. Christie, "A review of electroless deposition processes", Gold Bull., 1984, 17 (4), pages 118-127 (the teaching in which article is incorporated herein by reference).
- autocatalytic deposition means that the metal already deposited on the workpiece acts as a catalyst for further deposition of the same metal from the solution onto the workpiece.
- galvanic deposition for example copper deposition from an acidic solution onto an iron substrate, the more noble metal (Cu) replaces the less noble metal (Fe) on the surface. However, once the surface is covered with copper the reaction stops.
- galvanic (immersion) gold deposition baths the more noble metal (Au) replaces less noble metal, in particular either copper or nickel, on the surface of the component, until it is covered with gold, whereupon the reaction ceases.
- the maximum thickness of gold deposited by this method is 0.1-0.2 ⁇ m.
- An autocatalytic bath will deposit more metal on the same metal substrate and, in theory, assuming that all the operating parameters are within their limits, will continue to deposit the desired metal to an unlimited thickness.
- metal ions are reduced to metal atoms by electrons provided by the oxidation of a reducing agent.
- the oxidation consists of two steps: (1) BH4 ⁇ + H2O ⁇ BH3OH ⁇ + H2 (2) BH3OH ⁇ + H2O ⁇ BO2 ⁇ + H2
- Electroless deposition baths are prone to spontaneous decomposition, which is the sudden precipitation of metal ions from the solution as metal particles (sometimes known as "plating up").
- stabilisers in particular alkali metal cyanides such as KCN.
- Metallic impurities in the bath may also cause this decomposition and so chelating agents are added to complex any dissolved metals. Accelerators are often added to increase deposition rates.
- electroless gold deposition systems have hitherto still suffered from the problems of instability, in particular a variable rate of deposition (typically varying from 0 to 3 ⁇ m per hour) and a tendency to precipitate gold in bulk suddenly. Furthermore, such systems cannot be replenished and, therefore, are usually operated to exhaustion or until precipitation occurs.
- an electroless system which is stable, replenishable and capable of depositing gold of high purity at an acceptable rate. Desirably, such a system should be suitable for wire bonding and should have a robustness approaching that of the electroless copper or nickel systems already available, in order to reduce the demand on operator skill.
- the present invention provides an aqueous liquor for use as an electroless gold deposition bath, comprising a source of gold and a reducing agent, which liquor also contains a reduction-stabilising agent selected from (a) a mixture of an alkali metal or ammonium ferrocyanide and an alkali metal or ammonium ferricyanide, (b) 1-H-tetrazole, (c) redox mediators and (d) mixtures of any of these.
- a reduction-stabilising agent selected from (a) a mixture of an alkali metal or ammonium ferrocyanide and an alkali metal or ammonium ferricyanide, (b) 1-H-tetrazole, (c) redox mediators and (d) mixtures of any of these.
- the present invention also provides a method for the electroless deposition of gold, onto a surface of a substrate, from an aqueous liquor comprising a source of gold and a reducing agent, wherein the liquor also contains a reduction-stabilising agent selected from (a) a mixture of an alkali metal or ammonium ferrocyanide and an alkali metal or ammonium ferricyanide, (b) 1-H-tetrazole, (c) redox mediators and (d) mixtures of any of these.
- a reduction-stabilising agent selected from (a) a mixture of an alkali metal or ammonium ferrocyanide and an alkali metal or ammonium ferricyanide, (b) 1-H-tetrazole, (c) redox mediators and (d) mixtures of any of these.
- the present invention also provides an article having at least one surface onto which gold has been deposited by such a method.
- the aqueous liquor according to the present invention contains a source of gold in solution.
- any of the gold compounds, including salts and complexes, that have been used or proposed previously for use in electroless gold deposition (plating) solutions come into consideration, these including such compounds as MAu(CN)2, MAu(CN)4, MAu02 and MAu(0H)4 wherein M is ammonium or alkali metal, in particular potassium; M3Au(S03)2 wherein M is ammonium or alkali metal, in particular sodium; AuCN; and alkali metal gold imides, in particular potassium gold succinimide or potassium gold phthalimide.
- the alkali metal gold cyanides are particularly preferred, especially potassium gold cyanide, which may be represented by the formula KAu(CN)2.
- the gold compound may be formed in situ .
- any gold in the solution will, in effect, be present as a cyanide complex.
- Au III will tend to be converted into Au I in the solution.
- the liquor will have a gold concentration (expressed as elemental gold) of up to 10 g/l and it has been found that the concentration is desirably at least 0.25 g/l in order to achieve an acceptable deposition rate.
- gold concentrations as high as 3.5 g/l have been tested satisfactorily, the gold concentration is preferably maintained at a level of between 0.8 and 1 g/l in order to minimise the effects of dragout and to ensure a good distribution of the deposit.
- the aqueous liquor according to this invention also contains a reducing agent in solution.
- reducing agents have been proposed in the prior art for use in electroless gold plating solutions, including hypophosphites, formaldehyde, hydrazine and boron-based compounds such as borohydrides and amine boranes (eg. isopropyl amine borane, di- or tri-ethylamine borane and di- or tri-methylamine borane), although the amine boranes can be unpleasant to use and are expensive.
- the alkali metal borohydrides, especially potassium borohydride are preferred, these being particularly effective in conjunction with the alkali metal gold cyanides.
- the reducing agent will usually be present in an amount of 1 to 25 g/l, preferably 5 to 15 g/l.
- Potassium borohydride for example, may be used typically at a level of 5 to 21.6 g/l.
- the aqueous liquor also contains a reduction-stabilising agent, that is to say an agent that is intended to stabilise the reaction(s) whereby the gold is reduced in order to reduce or inhibit the tendency to random deposition varying from the very slow to the very sudden or even to the spontaneous precipitation of the gold.
- a reduction-stabilising agent that is to say an agent that is intended to stabilise the reaction(s) whereby the gold is reduced in order to reduce or inhibit the tendency to random deposition varying from the very slow to the very sudden or even to the spontaneous precipitation of the gold.
- the reduction-stabilising agent is generally employed in an amount of from 0.25 to 100 g/l, more usually 1 to 10 g/l.
- the aqueous liquor in certain preferred embodiments may contain in solution an alkali metal or ammonium ferricyanide and an alkali metal or ammonium ferrocyanide; the potassium compounds, K3Fe III (CN)6 and K4Fe II (CN)6, are preferred.
- the potassium compounds, K3Fe III (CN)6 and K4Fe II (CN)6, are preferred.
- 0.25 to 3 parts by weight of alkali metal or ammonium ferricyanide more preferably 0.4 to 2.5 parts by weight thereof, will be used per part by weight of alkali metal or ammonium ferrocyanide.
- potassium ferrocyanide and potassium ferricyanide for example, may be used typically at levels of, respectively, 1 to 50 g/l and 0.5-20 g/l.
- the aqueous liquor contains 1-H-tetrazole as a reduction-stabilising agent.
- 1-H-tetrazole - which may be used typically at levels of 1 to 10 g/l - may be used as the sole such agent, useful results have also been obtained using it in the presence of an alkali metal ferricyanide, especially K3Fe III (CN)6.
- Redox mediators oxidation-reduction mediators
- Redox mediators are known in biochemistry and cell biology as chemicals that promote transfer of electrons essential to the analysis of enzymes and tissues and have recently been proposed as additives in microbial fuel cells as they couple rich sources of electrons within micro organisms to an electrode (see J. Bennetto, "Microbes come to power", New Scientist, 16 April 1987, pages 36-39).
- Redox mediators which come into consideration are, for example, thionine (at a level, for example, of 1 to 5 g/l), resorufin (at a level, for example, of 1 to 5 g/l) and 1,10-phenanthroline (at a level, for example, of 0.25 to 1 g/l).
- ferrocyanide/ferricyanide mixtures may act as electron reservoirs thereby reducing or eliminating the tendency to spontaneous decomposition and thus may, like 1-H-tetrazole, act in a similar manner to the redox mediators in stabilising the gold-reduction (Au I ⁇ Au°) process.
- the pH of the aqueous liquor may be adjusted, as appropriate, for the deposition to proceed properly.
- an alkali metal borohydride as the reducing agent
- the pH of the liquor has not been found to be a critical parameter: as long as there are sufficient hydroxide ions for the formation of BH3OH ⁇ ions, the deposition reaction will proceed.
- an alkaline pH usually at least 11 and conveniently between 11 and 11.5, will in general be maintained when using such a borohydride, and may also be appropriate if a different reducing agent is employed.
- the liquor may contain alkali metal hydroxide, eg.
- sodium or potassium hydroxide which latter, for example, may be used typically at a level of 5 to 22.4 g/l
- a buffer salt may be used, such a buffer salt being selected, for example, from the alkali metal (especially sodium or potassium) orthophosphates, pyrophosphates, citrates, tartrates, borates and metaborates.
- an organic chelating agent which serves to complex or otherwise combine with metal ions present as impurities in the plating solution and thereby prevent their interference with the deposition or plating process.
- chelating agents are generally employed in an amount of from 0.1 to 100 g/l, preferably 1 to 20 g/l, and include ethylenediaminetetraacetic acid (EDTA) and the alkali metal salts thereof, diethylenetriaminepentaacetic acid and the alkali metal salts thereof, nitrilotriacetic acid and the alkali metal salts thereof, ethanolamine and triethanolamine.
- EDTA has been found to be particularly effective in complexing nickel in solution and may be used typically at a level of 1 to 10 g/l.
- Ethanolamine and triethanolamine may be used typically at levels of, respectively, 25-75 ml/l and 5-50 ml/l.
- the aqueous liquor according to the present invention will contain an alkali metal cyanide, such as sodium, potassium or lithium cyanide, in order to improve the stability of the source of gold, in particular when a gold cyanide complex is used.
- alkali metal cyanide such as sodium, potassium or lithium cyanide
- such cyanides are employed in an amount of 0.1 to 50 g/l, preferably 1 to 25 g/l.
- potassium cyanide is particularly preferred and may be used typically at a level of 5 to 22 g/l.
- glycine which may typically be used at a level of 1 to 10 g/l, acts as a chelating agent within the aqueous liquor.
- the aqueous liquor of the present invention may also contain an accelerator in order to improve the rate of deposition.
- an accelerator in order to improve the rate of deposition.
- water-soluble salts of semi-metals and metals of Groups IIIB, IVB and VB of the Periodic Table especially those elements in the 4th, 5th and 6th periods, such as thallium, lead or arsenic, may be used for this purpose, although in certain embodiments the presence of such an accelerator has increased the sensitivity of the bath to the presence of nickel contaminants.
- the concentration of the accelerator (expressed as elemental metal or semi-metal) will generally be from 0.001 to 500 mg/l, more usually 0.001 to 100 mg/l.
- Preferred accelerators are thallium (eg. as thallium sulfate), which can be used typically at a level of 0.001 to 7 mg/l (calculated on the elemental thallium), and lead (eg. as lead sulfate), which can be used typically at a level of 2 to 50 mg/l (calculated on the elemental lead).
- any of the specified components may be constituted by a mixture of two or more compounds of the appropriate description.
- the corresponding ammonium compounds may also come into consideration; however, the potassium compounds are usually the least expensive and the most readily available in high purity.
- the aqueous liquor of the present invention may be employed in conventional manner as an electroless gold deposition bath.
- the substrate to be plated will be immersed in the bath for a period of time sufficient to achieve a deposit of gold of the desired thickness.
- the substrate should present a catalytically active surface, especially a surface of a metal such as nickel, cobalt, iron, steel, palladium, platinum, copper, brass, manganese, chromium, molybdenum, tungsten, titanium, tin, silver, kovar and permalloy.
- a metal such as nickel, cobalt, iron, steel, palladium, platinum, copper, brass, manganese, chromium, molybdenum, tungsten, titanium, tin, silver, kovar and permalloy.
- nickel undercoat If a nickel undercoat is deemed necessary, it is recommended that nickel-boron type (ENi-B) electroless nickel deposits be used as the undercoat in preference to nickel-phosphorus type (ENi-P) electroless nickel deposits (since the present formulation will not deposit gold on the latter). If an ENi-P undercoat has to be used, it should be flashed with ENi-B prior to the electroless plating with gold.
- ENi-B nickel-boron type
- ENi-P nickel-phosphorus type
- a pre-dip containing potassium borohydride and potassium hydroxide (typically 5 g/l of each) has proven useful in accelerating the initiation of the gold deposition, protecting the gold bath from contamination and reducing the heat-sink effect of large components. Immersion of the substrate in the pre-dip for 1 minute at 80°C has been found to be suitable.
- Non-metallic substrates may be prepared for gold-plating in accordance with this invention by first rendering the surfaces thereof catalytically active, for example by the method described in US-A-3,589,916.
- the substrate is provided by an article that also comprises surfaces which do not require to be plated, it is possible to mask such surfaces in known manner, the masking material being removed after the plating step.
- Articles which may be gold-plated or gold-metallised in accordance with this invention include electronics components, especially those which have electrically isolated islands, pads and tracks, for example microwave components, chip carriers, printed circuit boards, integrated circuits and transistor headers.
- the gold deposition bath will normally be operated at a temperature of 80°C ⁇ 5°C. If the temperature exceeds 85°C, there may be a significant risk of spontaneous decomposition whereas below 75°C there is a significant reduction in the rate of gold deposition.
- the bath should be agitated, for example by magnetic stirring.
- the rate of stirring is from 200 to 600 rpm; higher rates of stirring may cause spontaneous decomposition, while lower rates of stirring will reduce the rate of gold deposition on the substrate.
- the components in the bath liquor may be replenished as appropriate.
- the source of gold will need to be replenished so as to maintain the concentration of gold at the required level.
- the gold compound added by way of replenishment need not be the same as the gold compound used in making up the initial liquor.
- Potassium borohydride decomposes rapidly at 80°C. Accordingly, when this reducing agent is used, it is desirable to analyse the bath every thirty minutes during operation and to replenish the potassium borohydride (the concentration of which typically decreases by 30% for each thirty minutes that the bath is at the working temperature), as appropriate.
- the accelerator if used, normally also requires to be replenished frequently.
- aqueous solutions were made up in a new, or at least scratch-free, beaker with carbon-treated demineralised water (the carbon treatment being effected in order to remove any colloidal polymer from the ion-exchange resin). Distilled water could have been used instead.
- a solution of the accelerator (if used), the reducing agent and a solution of the gold source were added, in that order and with stirring, to an aqueous liquor already containing the reduction-stabilising agent, chelating agent and auxiliary stabiliser(s). The solution was heated to 80°C and filtered if any particulate matter was visible therein.
- the exemplary formulations were investigated as electroless gold deposition baths using life tests on substrates provided (unless otherwise stated) as copper panels electroplated with pure gold to 2.5 ⁇ m and at a surface loading of 0.5 dm2/l, since at such a low loading any weaknesses in a system under test tend to be quickly revealed.
- the baths were operated at a temperature of 80°C ⁇ 4°C, with magnetic stirring with a PTFE coated stirrer at 400 rpm.
- the concentration of the reducing agent was analysed every 30 minutes and replenishment was effected with the required amount dissolved in the minimum quantity of carbon-treated demineralised water.
- the gold and other constituents were replenished after each 0.25 g of gold had been removed from solution. Filtration, through two glass-fibre filter papers under vacuum, was effected if particles of gold appeared on the bottom of the beaker or if the solution (initially an orange/yellow colour, turning to very pale yellow upon heating) turned light brown.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1 g/l potassium orthophosphate, K3PO4 12 g/l potassium cyanide, KCN 11 g/l potassium borohydride, KBH4 10.8 g/l monoethanolamine 50 ml/l potassium ferrocyanide 5 g/l potassium ferricyanide 2 g/l thallium (present as the sulfate) 2 mg/l
- the liquor was tested as an electroless gold-deposition bath and it was found that an acceptable rate of deposition (2.5-3.0 ⁇ m/h) could be achieved without precipitation (plating up) of gold into the liquor.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1 g/l potassium cyanide 11.0 g/l potassium hydroxide 11.2 g/l EDTA 5.0 g/l potassium borohydride 10.8 g/l potassium ferrocyanide 5.0 g/l potassium ferricyanide 2.0 g/l monoethanolamine 50 ml/l
- this liquor When tested, this liquor was found to provide a robust bath, which was resistant to nickel contamination.
- the deposition rates were, in general, about 1 ⁇ m/h. Initiation of deposition on nickel was found to take, in general, from 5 to 15 minutes; the contact with the nickel surface in this test did not cause spontaneous decomposition of the liquor.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1 g/l potassium cyanide 11.0 g/l potassium hydroxide 11.2 g/l EDTA 5.0 g/l potassium borohydride 10.8 g/l potassium ferrocyanide 5.0 g/l potassium ferricyanide 2.0 g/l triethanolamine 10.0 ml/l glycine 4.5 g/l
- this liquor provided a robust bath, resistant to nickel contamination.
- the gold turnover was between 150 and 200%, with a mean deposition rate of 2.5 ⁇ m/h. Initiation of the deposition on nickel was immediate; the contact with the nickel surface in this test did not cause spontaneous decomposition of the liquor.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1 g/l potassium cyanide 11 g/l potassium hydroxide 11.2 g/l potassium borohydride 10.8 g/l monoethanolamine 50.0 ml/l EDTA 5.0 g/l potassium ferrocyanide 5.0 g/l potassium ferricyanide 2.0 g/l thallium (present as the sulfate) 2.0 mg/l
- this aqueous liquor provided a robust, general purpose bath which proved particularly suitable for depositing gold on copper and copper alloys.
- the bath could normally be operated to 200-250% gold turnover, with a mean deposition rate of 2-2.5 ⁇ m/h, at a low loading of 0.5 dm2/l, the gold being replenished with further KAu(CN)2.
- Such replenishment was found to have no adverse effect on the free cyanide concentration.
- the potassium ferrocyanide, potassium ferricyanide, thallium and monoethanolamine were replenished as the bath was used, at rates of 1.25 g, 0.5 g, 0.5 mg and 2.5 ml respectively, per 0.25 g gold removed by deposition.
- the bath liquor did not spontaneously decompose when presented with a nickel surface. Initiation of the deposition on nickel was immediate.
- the bath liquor was, however, sensitive to soluble nickel contamination, it being found that a concentration of nickel of 10 mg/l could cause spontaneous decomposition. This sensitivity could be overcome by omitting the thallium from the solution.
- the deposits obtained from the baths of Examples 2, 3 and 4 were 99.9% pure gold (with 0.1% K) having a density of 19.3 g/cm3 and a hardness of between 90 and 95 HV.
- the deposits which were up to 30 ⁇ m in thickness were matt and lemon yellow (Examples 2 and 4) or orange-yellow (Example 3) in colour.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1.0 g/l potassium cyanide 11.0 g/l potassium hydroxide 11.2 g/l EDTA 5.0 g/l potassium borohydride 10.8 g/l monoethanolamine 50.0 ml/l thallium (present as the sulfate) 2.0 mg/l 1-H-tetrazole 1.0 g/l
- the liquor When tested as a gold plating bath, the liquor reached 188% gold turnover, with a mean deposition rate of 2.07 ⁇ m/h.
- the gold deposit was comparable in properties to those of the preceding Examples.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1.0 g/l potassium cyanide 11.0 g/l potassium hydroxide 11.2 g/l EDTA 5.0 g/l potassium borohydride 10.8 g/l monoethanolamine 50.0 ml/l potassium ferricyanide 2.0 g/l thallium (present as the sulfate) 2.0 mg/l 1-H-tetrazole 1.0 g/l
- the liquor When tested as a gold plating bath, the liquor reached 225% gold turnover, with a mean deposition rate of 2.05 ⁇ m/h.
- the gold deposit was comparable in properties to those of the preceding Examples.
- An aqueous liquor was prepared with the following formulation: gold (present as KAu(CN)2) 1.0 g/l potassium cyanide 11.0 g/l potassium hydroxide 11.2 g/l potassium borohydride 10.8 g/l
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888812329A GB8812329D0 (en) | 1988-05-25 | 1988-05-25 | Electroless deposition |
| GB8812329 | 1988-05-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0343816A1 true EP0343816A1 (de) | 1989-11-29 |
Family
ID=10637487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89304821A Withdrawn EP0343816A1 (de) | 1988-05-25 | 1989-05-12 | Verfahren zur stromlosen Metallabscheidung |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0343816A1 (de) |
| JP (1) | JPH0219473A (de) |
| KR (1) | KR890017391A (de) |
| GB (1) | GB8812329D0 (de) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338343A (en) * | 1993-07-23 | 1994-08-16 | Technic Incorporated | Catalytic electroless gold plating baths |
| EP0418715B1 (de) * | 1989-09-18 | 1994-08-17 | Hitachi, Ltd. | Lösung zur stromlosen Goldplattierung und Verfahren zur Goldplattierung mit dieser Lösung |
| EP0699778A1 (de) * | 1994-08-30 | 1996-03-06 | International Business Machines Corporation | Lösung und Verfahren zum Auffrischen von stromlosen Gold-Plattierungsbädern |
| EP4206357A1 (de) * | 2021-12-28 | 2023-07-05 | C. Uyemura & Co., Ltd. | Regenerationsverfahren für goldplattierungslösung |
| EP4407067A1 (de) | 2023-01-24 | 2024-07-31 | Atotech Deutschland GmbH & Co. KG | Plattierungsbadzusammensetzung zur plattierung von edelmetall und verfahren zur ablagerung einer edelmetallschicht |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6619563B2 (ja) * | 2015-04-30 | 2019-12-11 | 日本高純度化学株式会社 | 無電解金めっき液、アルデヒド−アミン付加体補給液及びそれらを用いて形成した金皮膜 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3485643A (en) * | 1966-05-06 | 1969-12-23 | Photocircuits Corp | Electroless copper plating |
-
1988
- 1988-05-25 GB GB888812329A patent/GB8812329D0/en active Pending
-
1989
- 1989-05-12 EP EP89304821A patent/EP0343816A1/de not_active Withdrawn
- 1989-05-22 JP JP1126824A patent/JPH0219473A/ja active Pending
- 1989-05-24 KR KR1019890006953A patent/KR890017391A/ko not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3485643A (en) * | 1966-05-06 | 1969-12-23 | Photocircuits Corp | Electroless copper plating |
Non-Patent Citations (1)
| Title |
|---|
| METAL FINISHING ABSTRACTS, vol. 16, no. 1, January/February 1974, page 24, right-hand column, abstract A; & SU-A-397 562 (INST. INORGAN. CHEM., ACAD. SCI.) 24-05-1971 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0418715B1 (de) * | 1989-09-18 | 1994-08-17 | Hitachi, Ltd. | Lösung zur stromlosen Goldplattierung und Verfahren zur Goldplattierung mit dieser Lösung |
| US5338343A (en) * | 1993-07-23 | 1994-08-16 | Technic Incorporated | Catalytic electroless gold plating baths |
| EP0699778A1 (de) * | 1994-08-30 | 1996-03-06 | International Business Machines Corporation | Lösung und Verfahren zum Auffrischen von stromlosen Gold-Plattierungsbädern |
| EP4206357A1 (de) * | 2021-12-28 | 2023-07-05 | C. Uyemura & Co., Ltd. | Regenerationsverfahren für goldplattierungslösung |
| EP4407067A1 (de) | 2023-01-24 | 2024-07-31 | Atotech Deutschland GmbH & Co. KG | Plattierungsbadzusammensetzung zur plattierung von edelmetall und verfahren zur ablagerung einer edelmetallschicht |
| WO2024156770A1 (en) | 2023-01-24 | 2024-08-02 | Atotech Deutschland GmbH & Co. KG | Plating bath composition for plating of precious metal and a method for depositing a precious metal layer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8812329D0 (en) | 1988-06-29 |
| KR890017391A (ko) | 1989-12-16 |
| JPH0219473A (ja) | 1990-01-23 |
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