Composition for metal plating comprising suppressing agent for void free submicron feature filling

Abstract

A composition for filling submicrometer sized features having an aperture size of 30 nanometers or less comprising a source of copper ions, and at least one suppressing agent selected from compounds of formula (I) wherein the R1 radicals are each independently selected from a copolymer of ethylene oxide and at least one further C3 to C4 alkylene oxide, said copolymer being a random copolymer. the R2 radicals are each independently selected from R1 or alkyl. X and Y are spacer groups independently, and X for each repeating unit independently, selected from C1 to C6 alkylen and Z—(O—Z)m wherein the Z radicals are each independently selected from C2 to C6 alkylen, n is an integer equal to or greater than 0. m is an integer equal to or greater than 1.

1 - 14 . (canceled) 
     
     
         15 . A process for electrodepositing copper on a substrate comprising at least one submicrometer sized feature having an aperture size of 30 nanometers or less, the process comprising
 a) contacting a copper plating bath comprising a copper ion source, at least one accelerator, and at least one suppressing agent of formula (I)   
       
         
           
           
               
               
           
         
         wherein 
         the R 1  radicals are each independently a random copolymer of ethylene oxide and at least one further C3 to C4 alkylene oxide, 
         the R 2  radicals are each independently R 1  or alkyl, 
         X and Y are spacer groups independently, and X for each repeating unit independently, selected from the group consisting of C1 to C6 alkylene and Z—(O—Z) m , wherein the Z radicals are each independently at least one C2 to C6 alkylene, 
         n is an integer equal to or greater than 0, 
         m is an integer equal to or greater than 1, and 
         wherein a content of ethylene oxide in the copolymer of ethylene oxide and the at least one further C3 to C4 alkylene oxide, is from 30 to 70%. 
         with the substrate, and 
         b) applying a current density to the substrate for a time sufficient to fill the at least one submicron size feature with copper. 
       
     
     
         16 . The process of  claim 15 , wherein X and Y are independently, and X for each repeating unit independently, a C1 to C4 alkylene. 
     
     
         17 . The process of  claim 15 , wherein an amine compound, comprised in reacted form in the at least one suppressing agent, is at least one selected from methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, hexylamine, dimethylamine, diethylamine, cyclopentylamine, cyclohexylamine, ethanolamine, diethanolamine, triethanolamine, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, neopentanediamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxyamidecane-1,13-diamine, triethylene glycol diamine, diethylene triamine, (3-(2-aminoethyl)aminopropylamine, 3,3′-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetraamine, and N,N′-bis(3-aminopropyl)ethylenediamine. 
     
     
         18 . The process of  claim 15 , wherein the C3 to C4 alkylene oxide comprises propylene oxide. 
     
     
         19 . The process of  claim 15 , wherein a molecular weight M w  of the suppressing agent is 6000 g/mol or more. 
     
     
         20 . The process of  claim 19 , wherein the molecular weight M w  of the suppressing agent is from 7000 to 19000 g/mol. 
     
     
         21 . The process of  claim 19 , wherein the molecular weight M w  of the suppressing agent is from 9000 to 18000 g/mol. 
     
     
         22 . The process of  claim 15 , wherein the suppressing agent comprises, in reacted form, at least one amine compound comprising at least 3 active amino groups. 
     
     
         23 . The process of  claim 15 , wherein the copper plating bath further comprises at least one leveling agent. 
     
     
         24 . The process of  claim 15 , wherein the features have an aspect ratio of 4 or more. 
     
     
         25 . The process of  claim 15 , wherein in the suppressing agent of formula (I), m is 1 to 10. 
     
     
         26 . The process of  claim 15 , wherein the C3 to C4 alkylene oxide consists essentially of propylene oxide. 
     
     
         27 . The process of  claim 16 , wherein an amine compound, comprised in reacted form in the at least one suppressing agent, is at least one selected from methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, hexylamine, dimethylamine, diethylamine, cyclopentylamine, cyclohexylamine, ethanolamine, diethanolamine, triethanolamine, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, neopentanediamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxyamidecane-1,13-diamine, triethylene glycol diamine, diethylene triamine, (3-(2-aminoethyl)aminopropylamine, 3,3′-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetraamine, and N,N′-bis(3-aminopropyl)ethylenediamine. 
     
     
         28 . The process of  claim 16 , wherein the C3 to C4 alkylene oxide comprises propylene oxide. 
     
     
         29 . The process of  claim 17 , wherein the C3 to C4 alkylene oxide comprises propylene oxide. 
     
     
         30 . The process of  claim 16 , wherein a molecular weight M w  of the suppressing agent is 6000 g/mol or more. 
     
     
         31 . The process of  claim 17 , wherein a molecular weight M w  of the suppressing agent is 6000 g/mol or more. 
     
     
         32 . The process of  claim 18 , wherein a molecular weight M w  of the suppressing agent is 6000 g/mol or more. 
     
     
         33 . The process of  claim 16 , wherein the suppressing agent comprises, in reacted form, at least one amine compound comprising at least 3 active amino groups. 
     
     
         34 . The process of  claim 17 , wherein the suppressing agent comprises, in reacted form, at least one amine compound comprising at least 3 active amino groups.