# US 2014/0197038 A1 · Copper electroplating solution and copper electroplating apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0197038 A1 - Document ID: US20140197038A1 - Status: Published application - Kind: A1 - Application number: 14/155,776 - Filed: 2014-01-15 - Published: 2014-07-17 - Earliest claimed: 2013-01-16 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Myung-Beom PARK; Yun-Deok KANG; Ki-Hyeon KIM; Youn-Joung CHO; Jung-Sik CHOI - Web page: https://patentgrep.com/patent/US20140197038A1 ## CPC - C25D 3/38: of copper - C25D 5/04: Electroplating with moving electrodes - C25D 5/08: Electroplating with moving electrolyte e.g. jet electroplating {(using locally applied jets of electrolyte C25D5/026)} - C25D 17/001: {Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells} - C25D 17/06: Suspending or supporting devices for articles to be coated - C25D 21/14: Controlled addition of electrolyte components - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR ## Abstract An electroplating solution includes an aqueous electrolyte solution including water soluble copper salts, sulfide ions and chloride ions, an accelerator including an organic material having sulfur (S), the accelerator accelerating copper (Cu) reduction, a suppressor including a polyether compound, the suppressor selectively suppressing the copper reduction, and a leveler including a water soluble polymer having nitrogen that is dissolved into positive ions in the aqueous electrolyte solution. ## Claims ### Claim 1 An electroplating solution comprising: an aqueous electrolyte solution including water soluble copper salts, sulfide ions and chloride ions; an accelerator including an organic material having sulfur (S), the accelerator accelerating copper (Cu) reduction; a suppressor including a polyether compound, the suppressor selectively suppressing the copper reduction; and a leveler including a water soluble polymer having nitrogen that is dissolved into positive ions in the aqueous electrolyte solution. ### Claim 2 (depends on 1) The electroplating solution of claim 1, wherein the aqueous electrolyte solution includes copper ions at a concentration of 10 g/L to 200 g/L, the sulfide ions at a concentration of 5 g/L to 50 g/L and the chloride ions at a concentration of 10 mg/L to 100 mg/L in the electroplating solution. ### Claim 3 (depends on 2) The electroplating solution of claim 2, wherein the leveler includes one of an N-vinyl pyrrolidone compound represented by Chemical Formula (1), a diallyldimethyl ammonium chloride (DADMAC) represented by Chemical Formula (2) and a copolymer of DADMAC and N-vinyl pyrrolidone represented by Chemical Formula (3) at a concentration of 0.1 g/L to 10 g/L in the electroplating solution, wherein each of R21 and R22 denote a C1-C4 unsubstituted alkyl group. ### Claim 4 (depends on 3) The electroplating solution of claim 3, wherein the leveler includes a copolymer of the N-vinyl pyrrolidone compound represented by Chemical Formula (1), the diallyldimethyl ammonium chloride (DADMAC) represented by Chemical Formula (2) and the copolymer of DADMAC and N-vinyl pyrrolidone represented by Chemical Formula (3). ### Claim 5 (depends on 3) The electroplating solution of claim 3, wherein the accelerator includes a disulfide compound represented by Chemical Formula (4), wherein each of R1 and R3 independently represent one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of R2 and R4 independently represent one of hydrogen (H), a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of Rm and Rn independently represent one of a C1-C10 alkylene, a C3-C10 cycloalkylene and a C4-C10 aromatic hydrocarbon, and each of M1+ and M2+ independently represent one of a proton, an alkali metal ion and an ammonium ion, and the suppressor includes a tri-block copolymer of polyethyleneoxide (PEO)-polypropyleneoxide (PPO)-PEO having a weight average molecular weight of 300 to 10,000 and having an ethylene oxide content (EO %) of 1% to 99% (w/w). ### Claim 6 An apparatus for electroplating copper on a substrate, comprising: a plating chamber containing an electroplating solution, the electroplating solution including, an aqueous electrolyte solution having water soluble copper salts, sulfide ions and chloride ions, an accelerator having an organic material having sulfur (S), the accelerator accelerating copper (Cu) reduction, a suppressor having a polyether compound, the suppressor selectively suppressing the copper reduction, and a leveler including a water soluble polymer having nitrogen that is dissolved into positive ions in the aqueous electrolyte solution; a dispersion plate uniformly dispersing the electroplating solution in the plating chamber and providing copper ions to the electroplating solution; a substrate holder electrically connected to the dispersion plate and to which a substrate is secured; and a solution provider providing the electroplating solution into the plating chamber. ### Claim 7 (depends on 6) The apparatus of claim 6, wherein the aqueous electrolyte solution includes copper ions at a concentration of 10 g/L to 200 g/L, the sulfide ions at a concentration of 5 g/L to 50 g/L and the chloride ions at a concentration of 10 mg/L to 100 mg/L in the electroplating solution, the leveler includes one of an N-vinyl pyrrolidone compound represented by Chemical Formula (1), a diallyldimethyl ammonium chloride (DADMAC) represented by Chemical Formula (2) and a copolymer of DADMAC and N-vinyl pyrrolidone represented by Chemical Formula (3) at a concentration of 0.1 g/L to 10 g/L in the electroplating solution, wherein each of R21 and R22 denote a C1-C4 unsubstituted alkyl group; the accelerator includes a disulfide compound represented by Chemical Formula (4), wherein each of R1 and R3 independently represent one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of R2 and R4 independently represent one of hydrogen (H), a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of Rm and Rn independently represent one of a C1-C10 alkylene, a C3-C10 cycloalkylene and a C4-C10 aromatic hydrocarbon, and each of M1+ and M2+ independently represent one of a proton, an alkali metal ion and an ammonium ion, and the suppressor includes a tri-block copolymer of polyethyleneoxide (PEO)-polypropyleneoxide (PPO)-PEO having a weight average molecular weight of 300 to 10,000 and having an ethylene oxide content (EO %) of 1% to 99% (w/w). ### Claim 8 (depends on 6) The apparatus of claim 6, wherein the dispersion plate includes a copper plate from which copper ions are dissolved into the electroplating solution and electrons remain therein due to a difference of electron affinity between copper of the copper plate and the positive ions in the electroplating solution, and the substrate holder includes a conductive plate electrically connected to the copper plate such that the electrons of the copper plate move to the conductive plate. ### Claim 9 (depends on 8) The apparatus of claim 8, wherein an external power is applied to an electrical circuit including the substrate holder and the dispersion plate such that a charge density on a surface of the substrate is in a range of 0.1 mA/cm2 to 300 mA/cm2. ### Claim 10 (depends on 6) The apparatus of claim 6, wherein the solution provider includes: a mixer configured to mix additives of the accelerator, the suppressor and the leveler with the aqueous electrolyte solution to thereby produce the electroplating solution, an additive reservoir connected to the mixer, the additive reservoir containing the additives, an ejecting pump configured to eject the electroplating solution from the mixer, and a flow line connected from the mixer to the plating chamber. ### Claim at position 11 11-15. (canceled) ### Claim 16 An electroplating solution comprising: an aqueous electrolyte solution including water soluble copper salts, sulfide ions and chloride ions; and a leveler including one of an N-vinyl pyrrolidone compound represented by Chemical Formula (1), a diallyldimethyl ammonium chloride (DADMAC) represented by Chemical Formula (2) and a copolymer of DADMAC and N-vinyl pyrrolidone represented by Chemical Formula (3), wherein each of R21 and R22 denote a C1-C4 unsubstituted alkyl group. ### Claim 17 (depends on 16) The electroplating solution of claim 16, wherein the aqueous electrolyte solution includes copper ions at a concentration of 10 g/L to 200 g/L, the sulfide ions at a concentration of 5 g/L to 50 g/L and the chloride ions at a concentration of 10 mg/L to 100 mg/L in the electroplating solution. ### Claim 18 (depends on 16) The electroplating solution of claim 16, wherein the leveler includes a copolymer of the N-vinyl pyrrolidone compound represented by Chemical Formula (1), the diallyldimethyl ammonium chloride (DADMAC) represented by Chemical Formula (2) and the copolymer of DADMAC and N-vinyl pyrrolidone represented by Chemical Formula (3). ### Claim 19 (depends on 16) The electroplating solution of claim 16, further comprising: an accelerator including a disulfide compound represented by Chemical Formula (4), wherein each of R1 and R3 independently represent one of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of R2 and R4 independently represent one of hydrogen (H), a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a trimethylsilyl group, each of Rm and Rn independently represent one of a C1-C10 alkylene, a C3-C10 cycloalkylene and a C4-C10 aromatic hydrocarbon, and each of M1+ and M2+ independently represent one of a proton, an alkali metal ion and an ammonium ion, and a suppressor including a tri-block copolymer of polyethyleneoxide (PEO)-polypropyleneoxide (PPO)-PEO having a weight average molecular weight of 300 to 10,000 and having an ethylene oxide content (EO %) of 1% to 99% (w/w). ### Claim 20 (depends on 19) The electroplating solution of claim 19, wherein the leveler is at a concentration of 0.1 g/L to 10 g/L in the electroplating solution, the accelerator is at a concentration of about 3 g/L to about 100 g/L in the electroplating solution, and the suppressor is at a concentration of about 10 g/L to about 500 g/L in the electroplating solution.