US3203878A - Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product - Google Patents
Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product Download PDFInfo
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- US3203878A US3203878A US170522A US17052262A US3203878A US 3203878 A US3203878 A US 3203878A US 170522 A US170522 A US 170522A US 17052262 A US17052262 A US 17052262A US 3203878 A US3203878 A US 3203878A
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- bath
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- copper
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- Expired - Lifetime
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- 229910052751 metal Inorganic materials 0.000 title claims description 22
- 239000002184 metal Substances 0.000 title claims description 22
- 238000009713 electroplating Methods 0.000 title claims description 20
- 239000002253 acid Substances 0.000 title description 17
- 239000007795 chemical reaction product Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000000654 additive Substances 0.000 claims description 35
- 230000000996 additive effect Effects 0.000 claims description 32
- 150000002739 metals Chemical class 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002659 electrodeposit Substances 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 6
- -1 thiourea radical Chemical class 0.000 description 47
- 229910052739 hydrogen Inorganic materials 0.000 description 33
- 239000001257 hydrogen Substances 0.000 description 33
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 229910052802 copper Inorganic materials 0.000 description 30
- 239000010949 copper Substances 0.000 description 30
- 125000001931 aliphatic group Chemical group 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005282 brightening Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 150000003460 sulfonic acids Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 150000001768 cations Chemical group 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 150000005840 aryl radicals Chemical class 0.000 description 8
- 125000004663 dialkyl amino group Chemical group 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009499 grossing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 241000933336 Ziziphus rignonii Species 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229940074993 carbon disulfide Drugs 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 240000000662 Anethum graveolens Species 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/21—Radicals derived from sulfur analogues of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/42—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/08—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- 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
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- organic sulfonic acids or their salts which contain at least one thiourea radical and at least one dithiocarbamic acid radical in the molecule, produce simultaneously excellent brightening and leveling eifects in acid metal electroplating baths, especially in copper electroplating baths.
- the employment of the agents according to the invention provides a substantial simplification of the baths with simultaneous improvement of the quality of the metal electroplates.
- These products possess excellent -full brightening and strong leveling properties, coupled with a temperature tolerance which is suificient tor all practical requirements, so that with the aid of these products the preparation and upkeep Of metal electroplating baths, especially of highsperformance bright copper electroplating baths, becomes substantial-1y simpler.
- the above-mentioned sulfonic acids can not only be employed in copper electroplating baths, in which they or their salts produce a particularly remarkable effect, but also to good advantage in electroplating baths which contain the salts of the metals zinc, lead, tin and cadmium or mixtures thereof.
- Another object is to provide a method and bath for electroplating wherein a single additive compound produces bright, level and non-porous electrodeposits of metals.
- the sulfonic acids or their salts which are employed in accordance with the present invention may be prepared in simple fashion by well known methods. In general, they are characterized by at least one dithiocarbamic acid group of the general formula in which R and R represent hydrogen or hydrocarbon radicals. Suitable such radicals are identical or different alkyl radicals which may possibly be substituted or, with inclusion of the nitrogen atom, may also together form a heterocyclic ring, such as a monpholine or piperazine ring, or also cycloalkyl radicals.
- the sul fonic acids according to the present invention "Ice are also characterized by at least one thiourea group of the general formula in which R and R represent hydrogen, alkyl radicals, cycloalkyl radicals, substituted or unsubstituted aryl radicals or also dithiocarbamic acid radicals attached to the nitrogen through an acyclic or cyclic intermediate mem her, as already described above.
- the sulfonic acids according to the present invention contain an alkyl sul-fonic acid group of the general formula in which R, is a low molecular alkyl radical with 1 to 4 carbon atoms. 7
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyiclic radicals wherein -R may be a tree valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals .
- R and R may join to fiorm a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals; Y is a member selected from the group consisting of :8 and X is selected from the group consisting of hydrogen and cation: n is a number at least 1.
- the R radical is 3 joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences. As indicated by the brackets, the R radical may be joined at more than one point in the molecule, such as to the R radical when it represents a free valence, or to the R radical when it is a dialky'larnino radical with a free valence on the nitrogen. R is also being joined to both open sulfur valences in Formula IV It is to be understood that the R radical always carries the sulfonic acid or sulfonate group.
- 0.5 mol of phenyl mustard oil was added dropwise at 30-35 C. to a solution of 0.5 mol of diethylene triamine in 300 cc. of ethanol, and the mixture was stirred for an additional two hours. Thereafter, 1 mol of sodium hydroxide dissolved in 150 cc. of water was added, and then 1 mol of carbon dis-ulfide was added dropwise to the solution at 40 C. The mixture was then stirred for twenty minutes while increasing the temperature to 60 C., and thereafter 1 mol of molten propane suiltone was added dropwise. After a few hours of boiling under reflux, the mixture was evaporated in vacuo.
- a further example of the sulfionic acids according to the present invention is 4-thiohexahydrod,3,5-triazinyll-ethyldithiocarbamic acid propylester-w-sultoni'c acid
- the sodium salt of this sulfionic acid was obtained by condensation of the sodium salt of aminoethyldithiocarbarnic acid propylesterw-sulfonic acid with thiourea and [formaldehyde with good yields in the for-m of a yellowish powder which had no melting point.
- This compound was prepared in the following manner: 13.6 gm. of the inner salt of Z-aminoethyldithio'carbamic acid were dissolved in 100 cc. of water. The resulting solution was admixed with 4 gm. of sodium hydroxide dissolved in 50 ml. of water, 7.6 gm. of thiourea were added and after the latter had dissolved 17.2 gm. of 35% formaldehyde solution were added over a period of evaporated in vacuo. The residue thus obtained was stirred for forty-five minutes and was then allowed to stand overnight, after which the clear green solution was evaporated in vacuo. The resldue thus obtained was taken up in 200 cc.
- This product was prepared as follows: a solution of 73 gm. of l-(B-aminoethyl)-2-cimidazolinethione, which had been prepared from thiourea and .diethy-lene triamine according to United States Patent No. 2,613,212, in 500 cc. of ethanol was admixed with a solution of 20.2 gm. of sodium hydroxide in cc. of water, 38.3 gm. of carbon di-sulfide were added dl'OPtWElSC in a temperature range of 35-40 C. and then 6 1.5 gm. of molten propane sultone were added slowly over a .period of twenty-five minutes at 6570 C.
- sulfonic acids or their salts which may be employed in accordance with the present invention are those in which the dithiocarbamic acid group is connected with that portion of the molecule which contains the thiourea and the sulfonic acid radical through an ester bond.
- An example of such a substance is the reaction product of N,N' bis (diethylthiocarbamyl-mercaptomethyl)-thiourea with propane sultone, which has the following formula:
- the linkage between the dithiocarbamic acid radical and the thiourea radical, which in the case of the above compound (No. 4) is formed by a methylene group, may also be formed by other groups, such as by an ethylene or propylene group or by another hydrocarbon radical, which may also be substituted or interrupted by hetero atoms or may be closed into a heterocyclic ring including the two nitrogen atoms, such as a piperazine ring.
- alkyl sulfonic acid radicals are attached to the.
- suitable sulfonic acids also include the following compounds which comprise the gm. per liter of N,N,N',N-tetraethyl-1,3-diaminopropanel-2.
- a bath having this composition produces uniformly full bright and satisfactory level copper electroplates in a current density range of 0.3 to 8 amp/dm. and at a temperature tolerance of 10 to 38 C.
- the copper electroplates are ductile and free from pores. They completely level a 280-grain etched area with a thickness of 20,11. without further additives.
- Example 11 0.1 gm. per liter of compound No. 8 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid, 1 gm. per liter of the addition product of mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture and 0.02 gm. per liter of thioflavin.
- a bath of this composition produces ductile, pore-free, uniformly full bright and satisfactorily leveling copper electroplates in a current density range of 0.2 to 8 amp/dm. at a temperature tolerance of 10 to 38 C.
- the agents according to the present invention are added to the electroplating bath in amounts of 50 mg. to 5 gm. per liter, preferably in amounts of 100 to 500 mg. per liter of bath fluid.
- the employment of the additives does not require special measures; they are readily soluble in the acid metal salt baths in the required quantity and also .exhibit satisfactory stability during the operation of the electroplating bath. If necessary, they may also be employed in combination with other known electroplating chemicals.
- Example I 0.2 gm. per liter of compound No. 4 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 80 gm. per liter of sulfuric acid, 2 gm. per liter of the addition product of 18 mols of ethylene oxide to 1 mol of nonylphenol and 0.25
- Example II When the acid electroplating bath described in Example II is modified with 0.11 gm. per liter of compound No. 7 as the brightening and leveling agent, the same good results as described in Example H are obtained.
- Example IV 0.20 gm. per liter of compound No. 2 are added to an acid copper plating bath which contains 220 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid and 1 gm. per liter of the addition product of 18 mols of ethylene oxide to 1 mol of nonylphenol.
- the addition of a further'component is not'necessary.
- the copper electroplates obtained thereby are ductile, free from pores, have a uniform full brightness and a good leveling efliect in the current density range of 0.2 to 8 amp/din. and at a temperature tolerance of 10 to 38 C.
- a 250-grain etching is completely leveled by a cop, per deposit 201:. thick.
- Example V 0.10 gm. per liter of compound No. 3 are added to an acid copper plating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, 60 gm. per liter of sulfuric acid and 1 gm. per liter of the addition product of 20 mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture.
- the addition of a further component is not necessary.
- Ductile, pore-free, uniformly full bright and satisfactorily leveling copper deposits are obtained in a current density range of 0.5 to 10 amp/dm. and rat a temperature tolerance of 10 to 38 C.
- a 280-grain etched area is completely leveled by a copper deposit of 20p thickness.
- Example V1 0.5 gm. per liter of compound No. 1 are added to an acid copper electroplating bath which contains 210 gm. per liter of copper sulfate, CuSO -5H O, and 60 gm. per liter of sulfuric acid.
- the addition of further assistants is not necessary because the bath having this simple composition already furnishes ductile, pore-free, uniformly tull bright and satisfactorily leveling copper electroplates (in a current density range of 0.5 to 8 amp/dm. at a temperature tolerance of 1-0 to 35 C.
- a ZZO-grain etched area is completely leveled by a copper deposit having a thickness of 20p. -A further advantage of this 'bath resides in that it can be operated without difiiculties with air.
- Example VII 0.4 gm. per liter of the compound No. 5 are added to an acid copper electroplating bath which contains 210 gm. per liter of copper sulfate, CuSO *5H O, and 60 gm. per liter of sulfuric acid. The addition of a further component is also unnecessary in this case. Ductile, pore-free, uniformly full bright and satisfactorily leveling copper electroplates are obtained in a current density range of 0.5 to 8 amp/dm. and at a temperature tolerance of 10 to 35 C. A 220-grain etched area is completely leveled by a copper deposit having a thickness of This bath can also be operated with air in an advantageous manner.
- Example VIII 0.15 gm. per liter of compound No. 5 is added to an acid zinc electroplating bath which contains 300 gm. per liter of zinc sulfate, 10 gm. per liter of aluminum sulfate
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals
- R is a lower alkyl radical
- R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring
- R is selected from the group consisting of aliphatic, dia'lkylamino, cycloaliphatic and lheterocyclic radicals
- Y is a member selected from the group consisting of Q and X is selected from the group consisting of hydrogen and
- the bath is operated in a pH range between 3 and 5 and furnishes bright, ductile, very fine-grained zinc electrodeposits which adhere well to the iron surface in a current density range of 0.5 to 8 amp/dm. at a temperature tolerance of 15 to 30 C.
- a process for producing bright, smooth deposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium which comprises depositing the metal from a bath containing the metal to be deposited in the form of an aqueous solution of an inorganic salt thereof in the presence of an additive compound having a structural formula selected from the group consisting of:
- Y is a member selected from the group consisting of S and X is selected from the group consisting of hydrogen and cations; and n is a number at least :1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive compound being present in sufficient amount to eifect said brightening and smoothing.
- a process for producing bright, smooth deposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium which comprises depositing the metal from a bath containing the metal to be deposited in the form of an aqueous solution of an inorganic saltthereof in the presence of about 100 to 500 rug/l. of bath of an additive compound having a structural formula selected from th group consisting of:
- R and R are selected from the group consisting 'lower alkyl radical;
- R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
- R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
- Y is a member selected from the group consisting of :S and SR 4O X
- X is selected from the group consisting of hydrogen and cations; and
- n is a number at least 1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive compound being present in sufficient amount to effect said brightening and smoothing.
- a process for producing bright, smooth deposits of copper which comprises depositing said copper from a bath containing an aqueous solution of an inorganic salt of copper in the presence of an additive compound having a structural formula selected from the group conll 2 nitrogen and sulfur atoms having free valences; said additive compound being present in suflicient amount to efiect said brightening and smoothing.
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence;
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
- R is a lower alkyl radical;
- R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
- R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
- Y is a member selected from .the group consisting of 8 and --SR SO X,,;
- X is selected from the group consisting of hydrogen and cations; and
- n is a number at least 1; said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences; said additive comp'ound
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals; Y is a member selected from the group consisting of :8 and -S--R SO X X is selected from the group consisting of hydrogen and cations; and n is a number at least 1; said R radical being joined to an valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may
- the bath of claim 18 wherein the additivecompound is: r 1 v wherein R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence; R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals; R is a lower alkyl radical; R is selected from the group consisting of hydrogen and aliphatic radicals wherein R aud R may join to form a heterocyclic ring; R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heterocyclic radicals;
- additive com- I Y is a member selected from the group consisting of Q and SR SO X X is selected from the group CH OH2 j I onr-on,
- An electroplating bath for producing bright, smooth electrodeposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium comprising an aqueous solution of an inorganic salt of the metal to be deposited and about mg. to 5 g./l. of bath of an additive compound having a structural formula selected from the group consisting of:
- An electroplating bath for producing bright, smooth electrodeposits of metals capable of being electrodeposited selected from the group consisting of copper, zinc, lead, tin and cadmium comprising an aqueous solution of an inorganic salt of the metal to be deposited and about to 500 mg./1. of bath of an additive compound having a structural formula selected from the group consisting of:
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocylic radicals wherein R may be a free valence;
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
- R; is a lower alkyl radical;
- R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
- R is selected from the group consisting of aliphatitic, dialkylamino, cycloaliphatic and heterocyclic radicals;
- Y is a member selected from the group consisting of :8 and S-,R SO X,,;
- X is selected from the group consisting of hydrogen and cations; and
- n is a number at least 1; said R -radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free val
- An electroplating bath for producing bright, smooth electrodeposits of copper comprising an aqueous solution of an inorganic salt of copper and an additive compound having a structural formula selected from .the group consisting of:
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and taken together, heterocyclic radicals wherein R may be a free valence;
- R and R are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aryl radicals;
- R is a lower alkyl radical;
- R is selected from the group consisting of hydrogen and aliphatic radicals wherein R and R may join to form a heterocyclic ring;
- R is selected from the group consisting of aliphatic, dialkylamino, cycloaliphatic and heteroeyclic radicals;
- Y is a member selected from .the group consisting of :S and -S--'R ---S0 X X is selected from the group consisting of hydrogen and cat-ions; and
- n is a number at least 1, said R radical being joined to an atom selected from the group consisting of nitrogen and sulfur atoms having free valences;
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DED35328A DE1146322B (de) | 1961-02-02 | 1961-02-02 | Saure galvanische Metallbaeder |
Publications (1)
Publication Number | Publication Date |
---|---|
US3203878A true US3203878A (en) | 1965-08-31 |
Family
ID=7042588
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US170522A Expired - Lifetime US3203878A (en) | 1961-02-02 | 1962-02-01 | Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product |
Country Status (7)
Country | Link |
---|---|
US (1) | US3203878A (zh) |
BE (1) | BE613365A (zh) |
CH (1) | CH427447A (zh) |
DE (1) | DE1146322B (zh) |
DK (1) | DK103053C (zh) |
GB (1) | GB928011A (zh) |
NL (2) | NL274211A (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3400059A (en) * | 1964-03-07 | 1968-09-03 | Dehydag Gmbh | Acidic copper electroplating baths and method |
US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
EP0068807A2 (en) * | 1981-06-24 | 1983-01-05 | M & T Chemicals, Inc. | Acid copper electroplating baths containing brightening and levelling additives |
US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
US4786746A (en) * | 1987-09-18 | 1988-11-22 | Pennsylvania Research Corporation | Copper electroplating solutions and methods of making and using them |
EP2128903A1 (en) * | 2008-05-30 | 2009-12-02 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of a metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)-group 13 (IIIA)-group 16 (VIA) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
US2948752A (en) * | 1959-05-18 | 1960-08-09 | Monsanto Canada Ltd | Combined fungistatic and bacteriostatic agents |
US3006954A (en) * | 1957-12-27 | 1961-10-31 | Shell Oil Co | Urea and thiourea compounds |
-
0
- NL NL134137D patent/NL134137C/xx active
- NL NL274211D patent/NL274211A/xx unknown
-
1961
- 1961-02-02 DE DED35328A patent/DE1146322B/de active Pending
- 1961-12-16 CH CH1462561A patent/CH427447A/de unknown
- 1961-12-28 GB GB46401/61A patent/GB928011A/en not_active Expired
-
1962
- 1962-02-01 US US170522A patent/US3203878A/en not_active Expired - Lifetime
- 1962-02-01 DK DK46962AA patent/DK103053C/da active
- 1962-02-01 BE BE613365A patent/BE613365A/fr unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
US3006954A (en) * | 1957-12-27 | 1961-10-31 | Shell Oil Co | Urea and thiourea compounds |
US2948752A (en) * | 1959-05-18 | 1960-08-09 | Monsanto Canada Ltd | Combined fungistatic and bacteriostatic agents |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3400059A (en) * | 1964-03-07 | 1968-09-03 | Dehydag Gmbh | Acidic copper electroplating baths and method |
US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
EP0068807A2 (en) * | 1981-06-24 | 1983-01-05 | M & T Chemicals, Inc. | Acid copper electroplating baths containing brightening and levelling additives |
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
EP0068807A3 (en) * | 1981-06-24 | 1984-07-25 | M & T Chemicals, Inc. | Acid copper electroplating baths containing brightening and levelling additives |
US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
US4786746A (en) * | 1987-09-18 | 1988-11-22 | Pennsylvania Research Corporation | Copper electroplating solutions and methods of making and using them |
EP2128903A1 (en) * | 2008-05-30 | 2009-12-02 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of a metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)-group 13 (IIIA)-group 16 (VIA) |
WO2009144036A1 (en) * | 2008-05-30 | 2009-12-03 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (ib)-group 13 (iiia) -group 16 (via) |
US20110094583A1 (en) * | 2008-05-30 | 2011-04-28 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (ib)-group 13 (iiia)-group 16 (via) |
US8828278B2 (en) | 2008-05-30 | 2014-09-09 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)—group 13 (IIIA)—Group 16 (VIA) |
Also Published As
Publication number | Publication date |
---|---|
DK103053C (da) | 1965-11-08 |
GB928011A (en) | 1963-06-06 |
DE1146322B (de) | 1963-03-28 |
NL134137C (zh) | |
BE613365A (fr) | 1962-05-29 |
CH427447A (de) | 1966-12-31 |
NL274211A (zh) |
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