US2707166A - Electrodeposition of copper from an acid bath - Google Patents
Electrodeposition of copper from an acid bath Download PDFInfo
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- US2707166A US2707166A US290091A US29009152A US2707166A US 2707166 A US2707166 A US 2707166A US 290091 A US290091 A US 290091A US 29009152 A US29009152 A US 29009152A US 2707166 A US2707166 A US 2707166A
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- United States
- Prior art keywords
- copper
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- liter
- sulfate
- bath
- 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.)
- Expired - Lifetime
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- 238000004070 electrodeposition Methods 0.000 title claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 28
- 229910052802 copper Inorganic materials 0.000 title description 28
- 239000010949 copper Substances 0.000 title description 28
- 239000002253 acid Substances 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 19
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003929 acidic solution Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 15
- 150000001450 anions Chemical group 0.000 description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- -1 amino, hydroxy Chemical group 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- QWUFXJHVFNRNCU-UHFFFAOYSA-N phenazin-1-amine Chemical compound C1=CC=C2N=C3C(N)=CC=CC3=NC2=C1 QWUFXJHVFNRNCU-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 210000000436 anus Anatomy 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical class CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000005184 naphthylamino group Chemical class C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- This invention relates to the electrodeposition of copper from an aqueous acidic bath and more particularly concerns the utilization of selected addition agents to aqueous acidic baths for the purposes hereinafter stated.
- the primary object of this invention is to decrease the grain size and increase the luster of the copper deposit without materially imparing the ductility of the plate or decreasing the current density range of the acidic copper plating bath.
- R1 and R2 may be hydrogen, methyl or ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted amino, hydroxy and alkoxy substituent groups.
- the anion X is relatively unimportant and in addition to the anions above given may be any one of a wide variety of other anions, including organic anions such as formate, acetate, propionate, etc. It will be appreciated that the compounds represented by the above formula, when present in an acid copper bath, are highly ionized substances and the anion X is in ionic admixture with the other anions of the bath such as the sulfate anion, the nitrate anion, etc. It is believed that the diamino phenylphenazonium nucleus or ion is the dominant contributor to the beneficial effects of decreasing the grain size without materially impairing ductility of the plate which is obtained from the presence in the bath of any of the compounds of Formula A.
- the phenyl or naphthyl radicals be substituted with amino or alkyl substituted amino groups, that the alkyl groups be either methyl or ethyl groups, and that the alkoxy group be methoxy or ethoxy; and for best bath life it is preferable to maintain a concentration of chloride, or its equivalent in bromide or iodide, of about .003 to about .020 gram/liter in the solution. It is to be understood that when X is either fluoride, sulfate, bisulfate or nitrate, that chloride, bromide or.
- iodide ions in an amount equivalent to about .003to .020 gram/liter of chloride is preferably present in addition.
- 2,707,166 Patented Apr. 26, 1955 contains a sutficient halide concentration, but it is usually preferable to replenish the halide during use in order to maintain the preferred minimum concentration of about .003 gram/liter of chloride or its equivalent.
- Janus Green B is the dye commercially known as Janus Green B.
- Janus Green B is sometimes designated Dia zine Green (Schultz #282) and chemically it may be designated briefly as diethyl-safranine-aZo-dimethyl-aniline.
- Another preferred example which is not generally as commercially available as Janus Green B, is represented by the above formula wherein R1 is hydrogen and R2 is a irfethyl radical, that is, dimethyl safranine azo dimethyl ani me.
- the extremely useful addition agents represented by Formula A which efiectively accomplish the above stated object may, in general, be classified as the product of the coupling reaction of a diazotized amino phenazine with phenol, naphthol or aryl amino compounds including the alkyl substitution products of phenol, naphthol, or aryl amino compounds.
- Janus Green B which is a diazotized amino phenazine coupled with dimethyl aniline, may be replaced by a diazotized amino phenazine coupled with other amino compounds such as substituted diethyl anilines and naphthylamines.
- the total concentration of the mixed dye in the acidic aqueous bath preferably approximates the concentration of any component as indicated in Table 1.
- Janus Green B may be mixed with Janus Black in a total concentration corresponding approximately to the concentration for either Janus Green B or Janus Black as given in Table 1.
- concentrations of the dyes of Table 1 falling within the range of .005 to .04 gram/liter represent preferred quantities.
- Janus Green B is commercially available in approximately 50% dye strength in admixture with an inorganic salt, but it is to be understood that the concentrations set forth herein and in the appended claims refer to dye strength.
- composition of the acidic copper bath may vary over rather wide limits, although for the best grain refinement, rate of brightening and for the widest bright plating range, the following composition, designated Formula taining proportions of addition agents indicated in Table 1 include controlled temperatures, bath agitation and cathode current densities.
- the bath temperatures may be from about 17 C. to 40 C. (approximately 70 F. to F.). Warmer temperatures above 40 C. tend to decrease the brightness of the plate, but temperatures up to 50 C. may be used satisfactorily.
- Cathode agitation and preferably uniform air agitation is desirable.
- dm. may be satisfactorily employed with the particular current density depending primarily upon the degree of agitation of the cathode film and the shape of the article to be plated.
- an average cathode current density of 30-50 amps/sq. ft. may be used.
- Formula B may include other ions for the purpose of increasing the conductivity of the solution such as sodium, potassium or ammonium ions. These ions are usually present in only minor concentrations.
- the copper sulfate of Formula B may be replaced by copper nitrate in approximately equivalent proportions, and when acidified with small amounts of phosphoric acid, nitric acid or sulfuric acid, the beneficial effect of reducing the grain size and increasing the luster of the deposit by additions of small concentrations of compounds of the type shown in Table 1 is also evident.
- the degree, however, of grain size, reduction and increase in luster is somewhat less extensive than is produced from the use of acidic baths made up primarily of copper sulfate.
- the beneficial effect of reducing the grain size and increasing the luster of the deposit by additions of small concentrations of compounds of the type shown in Table 1 is also evident.
- the degree, however, of grain size, reduction and increase in luster is somewhat less extensive than is produced from the use of acidic baths made up primarily of copper sulfate.
- the copper sulfate of Formula B may be replaced by copper nitrate in approximately equivalent proportions, and when acidified with small amounts of phosphoric acid, n
- copper sulfate or copper nitrate concentration in the bath may satisfactorily vary from as low as about 100 grams/liter up to saturation. Concentrations of acid above the equivalent in acidity of about 80-100 grams/ liter of sulfuric acid decrease the brightening effect of the addition agents represented by Formula A and are therefore to be avoided.
- wetting agents may be advantageously present in the baths of this invention.
- the surface-active compounds, sodium decyl sulfate and the sulfated mono-ethylene oxide condensate of decyl alcohol when present in small concentrations of about .01 to .06 gram/liter are effective in decreasing pitting and striation formation in the deposit due to the presence of harmful organic compounds or excessive concentrations of brighteners.
- These wetting agents normally cause excessive frothing with air agitation, but in the presence of the addition agents of Table l, the frothing is minimized.
- Example I CuSOaSHzQ 200 grams/liter. H2804 15 grams/liter. Janus Green B .003 gram/ liter. Temperature 70-95 F. Cathode current density 30-40 amps./ sq. ft.
- Example II CuSO4.5HzO 200 grams/liter. H2804; 15 grams/liter. Janus Black .01 gram/liter. Temperatureun 7090 F. Cathode current density 30.40 amps./ sq. ft.
- a bath for the electrodeposition of copper comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate, and minor proportions of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted ammo, hydroxy and alkoxy substituent groups.
- a bath for the electrodeposition of copper in the form of a fine grain deposit comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate and minor proportions of a compound selected from the group consisting of Janus Green, Janus Blue, Janus Black, Janus Gray, dimethyl safranine azo dimethyl aniline and mixtures thereof.
- a bath for the electrodeposition of copper comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate, and about .0015 to about .05 gram/liter of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl'substituted amino, hydroxy and alkoxy substituent groups.
- a bath for the electrodeposition of copper in the form of a time grain deposit comprising an aqueous acidic ride, bromide, iodide, fluoride, sulfate,
- a bath for the electrodeposition of copper comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate and a minor proportion of Janus Green B.
- a bath for the electrodeposition of copper comprisin g an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate and about .0015 to about .05 gram/liter of Janus Green B.
- a bath for the electrodeposition of copper in the form of a fine grain deposit comprising an aqueous acidic solution of copper sulfate and .005 to .04 gram/ liter of Janus Green B.
- aqueous acid copper solution containing a metal salt selected from the group consisting of copper sulfate and copper nitrate, said aqueous solution also containing minor proportions of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted amino,
- aqueous acidic copper solution containing a metal salt selected from the group consisting of copper sulfate and copper nitrate, said aqueous solution also containing minor proportions of a compound selected from a group consisting of Janus Green B, Janus Black, Janus Gray, Janus Blue, dimethylsafranine-azo-dimethyl-aniline and mixtures thereof.
- aqueous acidic copper solution containing a metal salt selected from the group consisting of copper sulfate and copper nitrate, said aqueous solution also containing about .00l5 to about .05 grams/liter of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and is an anion selected from the group consisting of chlobisulfate and nitrate, and Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted amino, hydroxy and alkoxy substituent groups.
- a bath for the electrodeposition of copper comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate, a halide selected from the group consisting of chloride, bromide and iodide in an amount equivalent ethyl radicals, X
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, phenyl and naphthyl radicals substituted with amino, and alkyl substituted amino, hydroxy and alkoxy substituent groups.
- the step which comprises electrolyzing an aqueous acidic copper solution containing a metal salt selected from the group consisting of copper sulfate and copper nitrate, a halide selected from the group consisting of chloride, bromide and iodide in an amount equivalent to about .003 gram/ liter to about .020 gram/liter of chloride and a minor proportion of a compound having the structure wherein R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals, X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate, and Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted amino, hydroxy and alkoxy substituent groups.
- a metal salt selected from the group consisting of copper
- a bath for the electrodeposition of copper comprising an aqueous acidic solution of a material selected from the group consisting of copper sulfate and copper nitrate, a halide selected from the group consisting of chloride, bromide and iodide in an amount equivalent to about .003 gram/liter to about .020 gram/liter of chloride, a minor proportion of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, phenyl and naphthyl radicals substituted with amino, and alkyl substituted amino, hydroxy and alkoxy substituent groups, and a small amount of a wetting agent.
- the step which comprises electrolyzing an aqueous acidic copper solution containing a metal salt selected from the group consisting of copper sulfate and copper nitrate, a halide selected from the group consisting of chloride, bromide and iodide in an amount equivalent to about .003 gram/- liter to about .020 gram/liter of chloride, a minor proportion of a compound having the structure:
- R1 and R2 are radicals selected from the group consisting of hydrogen, methyl and ethyl radicals
- X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfate, bisulfate and nitrate
- Z is an aromatic radical selected from the group consisting of phenyl, naphthyl, and phenyl and naphthyl radicals substituted with amino, alkyl substituted amino, hydroxy and alkoxy substituent groups and a small amount of a wetting agent.
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- 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)
- Electrolytic Production Of Metals (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL83873D NL83873C (de) | 1952-05-26 | ||
| NLAANVRAGE7804190,A NL178453B (nl) | 1952-05-26 | Werkwijze voor het elektrostatisch copieren. | |
| BE520209D BE520209A (de) | 1952-05-26 | ||
| US290091A US2707166A (en) | 1952-05-26 | 1952-05-26 | Electrodeposition of copper from an acid bath |
| GB13949/53A GB736252A (en) | 1952-05-26 | 1953-05-18 | Improvements in electrodeposition of copper from an acid bath |
| FR1077492D FR1077492A (fr) | 1952-05-26 | 1953-05-21 | Perfectionnements au dépôt électrolytique de cuivre à partir d'un bain acide |
| DEU2199A DE947656C (de) | 1952-05-26 | 1953-05-23 | Bad zur galvanischen Herstellung von Kupferueberzuegen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US290091A US2707166A (en) | 1952-05-26 | 1952-05-26 | Electrodeposition of copper from an acid bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2707166A true US2707166A (en) | 1955-04-26 |
Family
ID=23114498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US290091A Expired - Lifetime US2707166A (en) | 1952-05-26 | 1952-05-26 | Electrodeposition of copper from an acid bath |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2707166A (de) |
| BE (1) | BE520209A (de) |
| DE (1) | DE947656C (de) |
| FR (1) | FR1077492A (de) |
| GB (1) | GB736252A (de) |
| NL (2) | NL178453B (de) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2738318A (en) * | 1954-12-28 | 1956-03-13 | Udylite Res Corp | Electrodeposition of copper from an acid bath |
| US2842488A (en) * | 1954-11-05 | 1958-07-08 | Dehydag Gmbh | Process for the production of metal electrodeposits |
| US2882209A (en) * | 1957-05-20 | 1959-04-14 | Udylite Res Corp | Electrodeposition of copper from an acid bath |
| US3267010A (en) * | 1962-04-16 | 1966-08-16 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3288690A (en) * | 1962-04-16 | 1966-11-29 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
| US3743584A (en) * | 1970-06-06 | 1973-07-03 | Schering Ag | Acid bright copper plating bath |
| US4316778A (en) * | 1980-09-24 | 1982-02-23 | Rca Corporation | Method for the manufacture of recording substrates for capacitance electronic discs |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4469564A (en) * | 1982-08-11 | 1984-09-04 | At&T Bell Laboratories | Copper electroplating process |
| DE3420999A1 (de) * | 1983-06-10 | 1984-12-13 | Omi International Corp., Warren, Mich. | Waessriges saures galvanisches kupferbad und verfahren zur galvanischen abscheidung eines glaenzenden eingeebneten kupferueberzugs auf einem leitfaehigen substrat aus diesem bad |
| US4551212A (en) * | 1985-03-11 | 1985-11-05 | Rca Corporation | Bath and process for the electrodeposition of micromachinable copper and additive for said bath |
| US6709568B2 (en) | 2002-06-13 | 2004-03-23 | Advanced Technology Materials, Inc. | Method for determining concentrations of additives in acid copper electrochemical deposition baths |
| US20050067304A1 (en) * | 2003-09-26 | 2005-03-31 | King Mackenzie E. | Electrode assembly for analysis of metal electroplating solution, comprising self-cleaning mechanism, plating optimization mechanism, and/or voltage limiting mechanism |
| US20050109624A1 (en) * | 2003-11-25 | 2005-05-26 | Mackenzie King | On-wafer electrochemical deposition plating metrology process and apparatus |
| US20050194248A1 (en) * | 1999-04-13 | 2005-09-08 | Hanson Kyle M. | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US20050224370A1 (en) * | 2004-04-07 | 2005-10-13 | Jun Liu | Electrochemical deposition analysis system including high-stability electrode |
| US20050247576A1 (en) * | 2004-05-04 | 2005-11-10 | Tom Glenn M | Electrochemical drive circuitry and method |
| US20060102475A1 (en) * | 2004-04-27 | 2006-05-18 | Jianwen Han | Methods and apparatus for determining organic component concentrations in an electrolytic solution |
| US20060266648A1 (en) * | 2002-12-17 | 2006-11-30 | King Mackenzie E | Process analyzer for monitoring electrochemical deposition solutions |
| US20070108062A1 (en) * | 2003-11-19 | 2007-05-17 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| US7435320B2 (en) | 2004-04-30 | 2008-10-14 | Advanced Technology Materials, Inc. | Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions |
| US7438788B2 (en) | 1999-04-13 | 2008-10-21 | Semitool, Inc. | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US7872130B2 (en) | 2002-12-20 | 2011-01-18 | Atotech Deutschland Gmbh | Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit |
| US10982343B2 (en) | 2017-11-09 | 2021-04-20 | Atotech Deutschland Gmbh | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
| US11174566B2 (en) | 2017-06-16 | 2021-11-16 | Atotech Deutschland Gmbh | Aqueous acidic copper electroplating bath and method for electrolytically depositing of a copper coating |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005011708B3 (de) | 2005-03-11 | 2007-03-01 | Atotech Deutschland Gmbh | Polyvinylammoniumverbindung und Verfahren zu deren Herstellung sowie diese Verbindung enthaltende saure Lösung und Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2291590A (en) * | 1940-03-11 | 1942-07-28 | Harshaw Chem Corp | Electrodeposition of metals |
| US2326999A (en) * | 1940-03-11 | 1943-08-17 | Harshaw Chem Corp | Nickel plating |
| US2602774A (en) * | 1948-05-11 | 1952-07-08 | John F Beaver | Method of plating copper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2563360A (en) * | 1941-05-24 | 1951-08-07 | Gen Motors Corp | Electrodeposition of copper |
-
0
- NL NL83873D patent/NL83873C/xx active
- NL NLAANVRAGE7804190,A patent/NL178453B/xx unknown
- BE BE520209D patent/BE520209A/xx unknown
-
1952
- 1952-05-26 US US290091A patent/US2707166A/en not_active Expired - Lifetime
-
1953
- 1953-05-18 GB GB13949/53A patent/GB736252A/en not_active Expired
- 1953-05-21 FR FR1077492D patent/FR1077492A/fr not_active Expired
- 1953-05-23 DE DEU2199A patent/DE947656C/de not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2291590A (en) * | 1940-03-11 | 1942-07-28 | Harshaw Chem Corp | Electrodeposition of metals |
| US2326999A (en) * | 1940-03-11 | 1943-08-17 | Harshaw Chem Corp | Nickel plating |
| US2602774A (en) * | 1948-05-11 | 1952-07-08 | John F Beaver | Method of plating copper |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2842488A (en) * | 1954-11-05 | 1958-07-08 | Dehydag Gmbh | Process for the production of metal electrodeposits |
| US2905602A (en) * | 1954-11-05 | 1959-09-22 | Dehydag Gmbh | Production of metal electrodeposits |
| US2738318A (en) * | 1954-12-28 | 1956-03-13 | Udylite Res Corp | Electrodeposition of copper from an acid bath |
| US2882209A (en) * | 1957-05-20 | 1959-04-14 | Udylite Res Corp | Electrodeposition of copper from an acid bath |
| US3267010A (en) * | 1962-04-16 | 1966-08-16 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3288690A (en) * | 1962-04-16 | 1966-11-29 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
| US3743584A (en) * | 1970-06-06 | 1973-07-03 | Schering Ag | Acid bright copper plating bath |
| US4316778A (en) * | 1980-09-24 | 1982-02-23 | Rca Corporation | Method for the manufacture of recording substrates for capacitance electronic discs |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4469564A (en) * | 1982-08-11 | 1984-09-04 | At&T Bell Laboratories | Copper electroplating process |
| DE3420999A1 (de) * | 1983-06-10 | 1984-12-13 | Omi International Corp., Warren, Mich. | Waessriges saures galvanisches kupferbad und verfahren zur galvanischen abscheidung eines glaenzenden eingeebneten kupferueberzugs auf einem leitfaehigen substrat aus diesem bad |
| US4551212A (en) * | 1985-03-11 | 1985-11-05 | Rca Corporation | Bath and process for the electrodeposition of micromachinable copper and additive for said bath |
| US20050194248A1 (en) * | 1999-04-13 | 2005-09-08 | Hanson Kyle M. | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US7438788B2 (en) | 1999-04-13 | 2008-10-21 | Semitool, Inc. | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US20080217167A9 (en) * | 1999-04-13 | 2008-09-11 | Hanson Kyle M | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US7264698B2 (en) | 1999-04-13 | 2007-09-04 | Semitool, Inc. | Apparatus and methods for electrochemical processing of microelectronic workpieces |
| US6709568B2 (en) | 2002-06-13 | 2004-03-23 | Advanced Technology Materials, Inc. | Method for determining concentrations of additives in acid copper electrochemical deposition baths |
| US20060266648A1 (en) * | 2002-12-17 | 2006-11-30 | King Mackenzie E | Process analyzer for monitoring electrochemical deposition solutions |
| US7872130B2 (en) | 2002-12-20 | 2011-01-18 | Atotech Deutschland Gmbh | Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit |
| US20050067304A1 (en) * | 2003-09-26 | 2005-03-31 | King Mackenzie E. | Electrode assembly for analysis of metal electroplating solution, comprising self-cleaning mechanism, plating optimization mechanism, and/or voltage limiting mechanism |
| US20070108062A1 (en) * | 2003-11-19 | 2007-05-17 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| US7786303B2 (en) | 2003-11-19 | 2010-08-31 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| US20050109624A1 (en) * | 2003-11-25 | 2005-05-26 | Mackenzie King | On-wafer electrochemical deposition plating metrology process and apparatus |
| US20050224370A1 (en) * | 2004-04-07 | 2005-10-13 | Jun Liu | Electrochemical deposition analysis system including high-stability electrode |
| US20060102475A1 (en) * | 2004-04-27 | 2006-05-18 | Jianwen Han | Methods and apparatus for determining organic component concentrations in an electrolytic solution |
| US7427344B2 (en) | 2004-04-27 | 2008-09-23 | Advanced Technology Materials, Inc. | Methods for determining organic component concentrations in an electrolytic solution |
| US7435320B2 (en) | 2004-04-30 | 2008-10-14 | Advanced Technology Materials, Inc. | Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions |
| US7427346B2 (en) | 2004-05-04 | 2008-09-23 | Advanced Technology Materials, Inc. | Electrochemical drive circuitry and method |
| US20050247576A1 (en) * | 2004-05-04 | 2005-11-10 | Tom Glenn M | Electrochemical drive circuitry and method |
| US11174566B2 (en) | 2017-06-16 | 2021-11-16 | Atotech Deutschland Gmbh | Aqueous acidic copper electroplating bath and method for electrolytically depositing of a copper coating |
| US10982343B2 (en) | 2017-11-09 | 2021-04-20 | Atotech Deutschland Gmbh | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE947656C (de) | 1956-08-23 |
| GB736252A (en) | 1955-09-07 |
| NL178453B (nl) | |
| BE520209A (de) | |
| FR1077492A (fr) | 1954-11-08 |
| NL83873C (de) |
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