# US 8,771,495 B2 · Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,771,495 B2 - Document ID: US8771495B2 - Status: Granted - Kind: B2 - Application number: 13/785,946 - Filed: 2013-03-05 - Published: 2013-09-19 - Granted: 2014-07-08 - Earliest claimed: 2008-11-26 - Assignees: Enthone Inc. - Applicants: Enthone Inc. - Inventors: Vincent Paneccasio, Jr.; Xuan Lin; Richard Hurtubise; Qingyun Chen - Web page: https://patentgrep.com/patent/US8771495B2 ## CPC - H10W 20/057: {by selectively depositing, e.g. by using selective CVD or plating} - C25D 3/38: of copper - C25D 5/02: Electroplating of selected surface areas - C25D 7/123: {Semiconductors first coated with a seed layer or a conductive layer} - H10P 14/47: Electrolytic deposition, i.e. electroplating; Electroless plating - H10W 20/056: {by filling conductive material into holes, grooves or trenches} - H10W 20/4421: {the principal metal being copper} - H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10 - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A method and composition for metallizing a via feature in a semiconductor integrated circuit device substrate, using a leveler compound which is a dipyridyl compound. ## Claims ### Claim 1 An electrolytic deposition composition comprising: (a) a source of copper ions, and (b) a leveler compound, wherein the leveler compound comprises a polymer comprising repeating units that comprise quaternized dipyridyl moieties. ### Claim 2 (depends on 1) A composition as set forth in claim 1 wherein leveler compound has been formed by co-polymerization of a dipyridyl compound and an alkylating agent and repeat units of the polymer comprise one moiety derived from the dipyridyl compound and one moiety derived from the alkylating agent. ### Claim 3 An electrolytic deposition composition comprising: (a) a source of copper ions; and (b) a reaction product of a dipyridyl compound and an alkylating agent and the alkylating agent comprises the following structure (IIIb): Y—(CH2)p—B—(CH2)q—Z Structure (IIIb) wherein B is selected from among: and p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1; X is an integer from one to about four; Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; and R1 through R14 are each independently hydrogen, substituted or unsubstituted alkyl having from one to six carbon atoms, substituted or unsubstituted alkylene having from one to six carbon atoms, or substituted or unsubstituted aryl. ### Claim 4 (depends on 3) A composition as set forth in claim 3 wherein: p and q are both one or are both two; and B is selected from among: ### Claim 5 (depends on 3) A composition as set forth in claim 3 wherein: p and q are both one or are both two; and B is selected from among: ### Claim 6 (depends on 3) A composition as set forth in claim 3 wherein the alkylating agent is selected from the group consisting of 1-chloro-2-(2-chloroethoxy)ethane, 1,2-bis(2-chloroethoxy)ethane, 1,3-dichloropropan-2-one, 1,3-dichloropropan-2-ol, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,2-di(2-chloroethyl)ether, 1,4-bis(chloromethyl)benzene, m-di(chloromethyl)benzene, and o-di(chloromethyl)benzene. ### Claim 7 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises the following structure (I): wherein R1 is a moiety that connects the pyridine rings. ### Claim 8 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises the following structure (Ia): wherein h is an integer from 0 to 6, and R2 and R3 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms. ### Claim 9 (depends on 8) The method of claim 8 wherein R2 and R3 are each hydrogen, and the dipyridyl compound comprises the general structure (IIa): wherein m is an integer from 0 to 6. ### Claim 10 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises any of the following structures (IIb) through (IId): wherein m is an integer from 0 to 6. ### Claim 11 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises structure (IIe) or (IIf): ### Claim 12 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises the following structure (Ib): wherein i and j are integers from 0 to 6, and R4, R5, R6, and R6 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms. ### Claim 13 (depends on 12) The method of claim 12 wherein i and j are both 0, and the dipyridyl compound comprises one of the following structures: ### Claim 14 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises the following structure (Ic): wherein k and l are integers from 0 to 6, and R8, R9, R10, R11, and R12 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms. ### Claim 15 (depends on 3) The method of claim 3 wherein the dipyridyl compound comprises the following structure (Id): ### Claim 16 A composition for metalizing a via feature in a semiconductor integrated circuit device substrate comprising: (a) a source of copper ions; (b) a leveler compound comprising the reaction product of a dipyridyl compound and an alkylating agent, wherein the dipyridyl compound comprises structure (IIf): (c) an accelerator; and (d) a suppressor. ### Claim 17 A composition for metalizing a via feature in a semiconductor integrated circuit device, the composition comprising: (a) a source of copper ions; (b) a leveler compound comprising the following structure (XIX): wherein o is one or two; and A is selected from among: Y is selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, dimethyl sulfonate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; and m is an integer having a value between one and six; (c) an accelerator; and (d) a suppressor. ### Claim 18 (depends on 17) A composition as set forth in claim 17 wherein leveler compound comprises the following structure (XX): ### Claim 19 (depends on 17) A composition as set forth in claim 17 wherein the leveler compound comprises the following structure (XXI):