Composition for copper plating and associated methods

Abstract

A composition for copper plating and associated methods, a method of forming a copper wiring including forming an insulation layer having a recessed portion on a substrate, and forming a copper layer on the insulation layer to fill the recessed portion by performing an electroplating process using a composition that includes an aqueous electrolyte solution containing a copper ion and at least one of a disulfide compound represented by Formula 1, a betaine compound represented by at least one of Formulae 3 and 4, and a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) having a weight average molecular weight of about 2,500 to about 5,000 g/mol and an ethylene oxide content (EO %, w/w) of about 30% to about 60%.

1 . A method of forming a copper wiring, the method comprising:
 forming an insulation layer having a recessed portion on a substrate; and   forming a copper layer on the insulation layer to fill the recessed portion by performing an electroplating process using a composition that includes an aqueous electrolyte solution containing a copper ion and at least one of a disulfide compound represented by Formula 1, a betaine compound represented by at least one of Formulae 3 and 4, and a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO),   
       
         
           
           
               
               
           
         
         wherein:
 in Formula 1, R 1  and R 3  are each independently substituted or unsubstituted C 1 -C 10  alkyl, cycloalkyl, aromatic hydrocarbon, or alkylsilyl, R 2  and R 4  are each independently hydrogen, C 1 -C 10  alkyl, cycloalkyl, aromatic hydrocarbon, or alkylsilyl, Rm and Rn are each independently a C 1 -C 10  alkylene chain, a C 3 -C 10  cycloalkylene chain, or a C 4 -C 10  aromatic hydrocarbon chain, and M 1   +  and M 2   +  are each independently a hydrogen ion, an alkali metal ion, or an ammonium ion, 
 in Formulae 3 and 4, R 7  and R 10  are each independently C 1 -C 20  alkyl, cycloalkyl or aromatic hydrocarbon, R 8 , R 9 , R 11 , and R 12  are each independently C 1 -C 4  alkyl, and n is an integer of 1 to about 10, and 
 the triblock copolymer of PEO-PPO-PEO has a weight average molecular weight of about 2,500 to about 5,000 g/mol and an ethylene oxide content (EO %, w/w) of about 30% to about 60%. 
 
       
     
     
         2 . The method as claimed in  claim 1 , wherein:
 the composition includes the disulfide compound represented by Formula 1, and   the disulfide compound is a compound represented by Formula 2,   
       
         
           
           
               
               
           
         
         wherein R 5  and R 6  are each independently methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or trialkylsilyl, and M 1   +  and M 2   +  are each independently a hydrogen ion, an alkali metal ion, or an ammonium ion. 
       
     
     
         3 . The method as claimed in  claim 1 , wherein:
 the composition includes the PEO-PPO-PEO triblock copolymer, and   the PEO-PPO-PEO triblock copolymer has a weight average molecular weight of about 2,500 to about 3,500 g/mol.   
     
     
         4 . The method as claimed in  claim 1 , wherein:
 the composition includes the betaine compound represented by at least one of Formulae 3 and 4, and   in Formulae 3 and 4, R 7  and R 10  are each independently C 6 -C 20  alkyl.   
     
     
         5 . The method as claimed in  claim 1 , wherein:
 the composition includes the betaine compound represented by at least one of Formulae 3 and 4, and   the betaine compound represented by at least one of Formulae 3 and 4 includes at least one of lauryl dimethyl betaine and lauramidopropyl dimethyl betaine.   
     
     
         6 . The method as claimed in  claim 1 , further comprising forming a diffusion barrier layer on the insulation layer having the recessed portion. 
     
     
         7 . The method as claimed in  claim 1 , further comprising forming a seed layer on the diffusion barrier layer, wherein the copper layer is formed on the seed layer to fill the recessed portion. 
     
     
         8 . The method as claimed in  claim 1 , wherein the aqueous electrolyte solution further includes a halide ion. 
     
     
         9 . A method of forming a copper wiring, the method comprising:
 forming a first insulation layer on the substrate having a conductive structure, the first insulation layer including a first opening exposing the conductive structure;   forming a second insulation layer on the first insulation layer, the second insulation layer including a second opening exposing the first opening;   forming a diffusion barrier layer along the first opening and the second opening;   forming a seed layer on the diffusion barrier layer;   forming a copper layer on the seed layer to fill the first opening and the second opening by performing an electroplating process using a composition that includes an aqueous electrolyte solution containing a copper ion and at least one of a disulfide compound represented by Formula 1, a betaine compound represented by at least one of Formulae 3 and 4, and a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO),   
       
         
           
           
               
               
           
         
         wherein:
 in Formula 1, R 1  and R 3  are each independently substituted or unsubstituted C 1 -C 10  alkyl, cycloalkyl, aromatic hydrocarbon, or alkylsilyl, R 2  and R 4  are each independently hydrogen, C 1 -C 10  alkyl, cycloalkyl, aromatic hydrocarbon, or alkylsilyl, Rm and Rn are each independently a C 1 -C 10  alkylene chain, a C 3 -C 10  cycloalkylene chain, or a C 4 -C 10  aromatic hydrocarbon chain, and M 1   + and M 2   +  are each independently a hydrogen ion, an alkali metal ion, or an ammonium ion, 
 in Formulae 3 and 4, R 7  and R 10  are each independently C 1 -C 20  alkyl, cycloalkyl or aromatic hydrocarbon, R 8 , R 9 , R 11 , and R 12  are each independently C 1 -C 4  alkyl, and n is an integer of 1 to about 10, and 
 
         the triblock copolymer of PEO-PPO-PEO has a weight average molecular weight of about 2,500 to about 5,000 g/mol and an ethylene oxide content (EO %, w/w) of about 30% to about 60%. 
       
     
     
         10 . The method as claimed in  claim 9 , wherein the first opening has a hole shape and the second opening has a trench shape. 
     
     
         11 . The method as claimed in  claim 9 , wherein the conductive structure is a portion of the substrate doped with impurities. 
     
     
         12 . The method as claimed in  claim 9 , wherein the conductive structure is one of a pad or a conductive line formed on the substrate. 
     
     
         13 . The method as claimed in  claim 9 , wherein the composition includes the disulfide compound represented by Formula 1. 
     
     
         14 . The method as claimed in  claim 9 , wherein the aqueous electrolyte solution further includes a halide ion. 
     
     
         15 - 17 . (canceled)