US3400059A - Acidic copper electroplating baths and method - Google Patents
Acidic copper electroplating baths and method Download PDFInfo
- Publication number
- US3400059A US3400059A US423822A US42382265A US3400059A US 3400059 A US3400059 A US 3400059A US 423822 A US423822 A US 423822A US 42382265 A US42382265 A US 42382265A US 3400059 A US3400059 A US 3400059A
- Authority
- US
- United States
- Prior art keywords
- bath
- leveling
- group
- copper
- chlorine
- 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
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 22
- 229910052802 copper Inorganic materials 0.000 title description 20
- 239000010949 copper Substances 0.000 title description 20
- 238000000034 method Methods 0.000 title description 17
- 238000009713 electroplating Methods 0.000 title description 10
- 230000002378 acidificating effect Effects 0.000 title description 2
- 239000000654 additive Substances 0.000 description 19
- -1 thiourea radical Chemical class 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 238000005282 brightening Methods 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002659 electrodeposit Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241000272534 Struthio camelus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 241000054822 Lycaena cupreus Species 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
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YSSAGHQOEYPLQO-UHFFFAOYSA-N propyl n,n-diethylcarbamodithioate Chemical compound CCCSC(=S)N(CC)CC YSSAGHQOEYPLQO-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B61—RAILWAYS
- B61D—BODY DETAILS OR KINDS OF RAILWAY VEHICLES
- B61D3/00—Wagons or vans
- B61D3/16—Wagons or vans adapted for carrying special loads
- B61D3/18—Wagons or vans adapted for carrying special loads for vehicles
- B61D3/182—Wagons or vans adapted for carrying special loads for vehicles specially adapted for heavy vehicles, e.g. public work vehicles, trucks, trailers
- B61D3/184—Wagons or vans adapted for carrying special loads for vehicles specially adapted for heavy vehicles, e.g. public work vehicles, trucks, trailers the heavy vehicles being of the trailer or semi-trailer type
-
- 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
- a further object is to provide additives for an acid copper electroplating process and bath whereby level electrodeposits may be obtained when using ordinary tap water.
- the compounds used in the baths have the formula wherein R and R are selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and together with N an aromatic heterocyclic residue, and R is selected from the group consisting of hydrogen, alkyl, cycloaliphatic aromatic and the group as above defined.
- the compounds used according to the invention may be prepared in a simple manner according to methods well known. They may be combined in the acid electroplating copper baths with the usual additives, especially with brightening agents. Especially satisfactory brightening agents have proven to be compounds which have at least one carbon atom exclusively surrounded by hetero atoms, to which a bivalent aliphatic or aromatic radical,
- N,N-diethyl-thiocarbamylmercaptomethyl-N'-phenylthiourea presents the best results in customary baths with high chlorine-ion concentration as well as in those which contain the specific brightening agents indicated above.
- the leveling agents used according to the invention are added in quantities of 0.001 to 20 g./l., preferably of 0.01 to 0.5 g./l. of bath liquor.
- the brightening agents, considered as especially favorable for the combination are added in a quantity of 0.05 to 5 g./l., preferably 0.1 to 0.5 g./l. of bath liquor.
- the copper-plating process is conducted in the generally customary temperatureand current density ranges.
- Example I l g./l. of the addition product of 13 mol of ethylene -mercapto-methyl-N-phenyl-thiourea with propansultone
- Example IV 0.4 g./l. of the reaction product of N,N-dietl1yl-thiocarbamyl-mercaptornethyl-N-phenylthiourea with propansultone were added to an acid copper bath of the same basic composition as in Example I.
- Example V An air agitated copper bath of the basic composition as in Example I with an addition of 0.08 g./l.
- Example 11 1 g./l. of the addition product of 18 mol of ethylene oxide to 1 mol of nonephenol as a wetting agent, 0.25 g./l. of the reaction product of N,N-bis-(diethyl-thiocarbamyl-mercaptomethyl)-thiourea with propansultone as a brightening agent and 0.1 g./l. of the compound No. l were added to an acid copper plating bath of the same composition as in Example I having a chlorine-ion concentration of 250 mg./l. The bath furnished, at a temperature tolerance of 10 to 35 C. in the current density range of 0.5 to 8 amp/dm.
- Example III 1 g./l. of the addition product of 18 mol of ethylene oxide in 1 mol of nonylphenyl as a wetting agent and 0.1 g./l. of the reaction product of N,N-dicthyl-thiocarbamylductile, pore-free glossy copper precipitates, which were not leveled, however.
- An acid copper electroplating bath for obtaining level electrodeposits comprising an aqueous solution of an inorganic copper salt and having a chlorine-ion concentration above 60 mg./l., containing as a leveling additive from 0.001 to 20 g./l. of an organic compound, of the formula S S R1 wherein R and R are selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and together with N an aromatic heterocyclic residue and R is selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and the group as above defined.
- the bath of claim 1 which further contains compounds as brightening agents having at least one carbon atom exclusively surrounded by hetero atoms, a member 5 selected from the group consisting of a bivalent aliphatic and aromatic radical with a sulfonic acid group being bound to said'carbon atom through a member selected from the group consisting of sulfur and nitrogen.
- leveling additive is 1 '-C2H5 Q NHCNHCIIz-SCN H II S S (4H5 5.
- leveling additive is C2115 CzHs /NC S--CHzNHfi-NH-CHzS-CN C9115 S S S ⁇ C2H5 6.
- leveling additive is CHr-CH:
- the leveling additive is CHe-CHa CHZ-CHfl N(
- the leveling additive is CHz-CH2 C2115 CH1 /CHNHfiNHOH-SQ-N oHz-o'rn s s C2Hn 9.
- the leveling additive is NH2C-NH-CH2SCN II I! S OH:
- An acid copper electroplating bath for obtaining level electrodeposits comprising an aqueous solution of an inorganic copper salt and having a chlorine-ion concentration above 60 mg./l., containing as a leveling additive from 0.01 to 0.5 g./l. an organic compound of the formula wherein R and R are selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and togetherwith N an aromatic heterocyclic residue and R is selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and the group NOSCH;- ll R1 s as above defined.
- a process for obtaining level copper electrodeposits from an acid copper electroplating bath comprising an aqueous solution of an inorganic copper salt and having a chlorine-ion concentration above 60 mg./l., containing as a leveling additive from 0.001 to 20 g./l. of an organic compound, of the formula R RzNH(IIJNHCHzS(FIN wherein R and R are selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and together .with N an aromatic heterocyclic residue and R is selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and the group /NCSCH- R1 S as above defined.
- leveling additive 15. The process of claim 12, wherein the leveling additive is 16. The process of claim 12 wherein the leveling additive is 17. The process of claim 12 wherein the leveling additive is 18. The process of claim 12 wherein the leveling additive is 19. The process of claim 12 wherein the leveling additive is our-on, out CHNH(!?NH-CHSCIN 20. The process of claim 12 wherein the leveling additive is S OH:
- R and R are selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and together with N an aromatic heterocyclic residue and R is selected from the group consisting of hydrogen, alkyl, cycloaliphatic, aromatic and the group as above defined.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED43821A DE1248415B (de) | 1964-03-07 | 1964-03-07 | Saure galvanische Kupferbaeder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3400059A true US3400059A (en) | 1968-09-03 |
Family
ID=7047882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US423822A Expired - Lifetime US3400059A (en) | 1964-03-07 | 1965-01-06 | Acidic copper electroplating baths and method |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3400059A (d) |
| AT (1) | AT254647B (d) |
| BE (1) | BE660606A (d) |
| BR (1) | BR6567577D0 (d) |
| CH (1) | CH450859A (d) |
| DE (1) | DE1248415B (d) |
| FR (1) | FR1425983A (d) |
| GB (1) | GB1036579A (d) |
| NL (1) | NL147194B (d) |
| SE (1) | SE303075B (d) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US20080121527A1 (en) * | 2002-03-05 | 2008-05-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US9493884B2 (en) | 2002-03-05 | 2016-11-15 | Enthone Inc. | Copper electrodeposition in microelectronics |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030199B (zh) * | 2020-08-27 | 2021-11-12 | 江苏艾森半导体材料股份有限公司 | 一种用于先进封装的高速电镀铜添加剂及电镀液 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US3122549A (en) * | 1961-07-08 | 1964-02-25 | Dehydag Gmbh | Novel organic sulfonic acids having dithiocarbamic acid ester and thiourea or thiosemicarbazide groups and their salts and preparation thereof |
| US3203878A (en) * | 1961-02-02 | 1965-08-31 | Dehydag Deutsche Hydriewerke G | Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product |
| US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
-
1964
- 1964-03-07 DE DED43821A patent/DE1248415B/de active Pending
-
1965
- 1965-01-06 US US423822A patent/US3400059A/en not_active Expired - Lifetime
- 1965-02-04 GB GB4814/65A patent/GB1036579A/en not_active Expired
- 1965-02-05 NL NL656501501A patent/NL147194B/xx not_active IP Right Cessation
- 1965-03-04 BR BR167577/65A patent/BR6567577D0/pt unknown
- 1965-03-04 BE BE660606D patent/BE660606A/xx unknown
- 1965-03-05 AT AT195065A patent/AT254647B/de active
- 1965-03-05 SE SE2879/65A patent/SE303075B/xx unknown
- 1965-03-05 CH CH310965A patent/CH450859A/de unknown
- 1965-03-05 FR FR8188A patent/FR1425983A/fr not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US3203878A (en) * | 1961-02-02 | 1965-08-31 | Dehydag Deutsche Hydriewerke G | Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product |
| US3122549A (en) * | 1961-07-08 | 1964-02-25 | Dehydag Gmbh | Novel organic sulfonic acids having dithiocarbamic acid ester and thiourea or thiosemicarbazide groups and their salts and preparation thereof |
| US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US20080121527A1 (en) * | 2002-03-05 | 2008-05-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US9222188B2 (en) * | 2002-03-05 | 2015-12-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US9493884B2 (en) | 2002-03-05 | 2016-11-15 | Enthone Inc. | Copper electrodeposition in microelectronics |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1248415B (de) | 1967-08-24 |
| GB1036579A (en) | 1966-07-20 |
| SE303075B (d) | 1968-08-12 |
| FR1425983A (fr) | 1966-01-24 |
| NL6501501A (d) | 1965-09-08 |
| CH450859A (de) | 1968-04-30 |
| BR6567577D0 (pt) | 1973-12-27 |
| NL147194B (nl) | 1975-09-15 |
| BE660606A (d) | 1965-09-06 |
| AT254647B (de) | 1967-05-26 |
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