Composition for copper bump electrodeposition comprising a leveling agent

Abstract

Disclosed herein is a composition including copper ions and at least one additive including a polyalkyleneimine backbone including N-hydrogen atoms, where(a) the polyalkyleneimine backbone has a mass average molecular weight MW of from 600 g/mol to 100 000 g/mol,(b) the N-hydrogen atoms are each substituted by a polyoxyalkylene group including an oxyethylene and a C3 to C6 oxyalkylene unit, and(c) the average number of oxyalkylene units in the polyoxyalkylene groups is of from more than 10 to less than 30 per N-hydrogen atom in the polyalkyleneimine.

1 . A composition comprising copper ions and at least one additive comprising a polyalkyleneimine backbone comprising N-hydrogen atoms, wherein
 (a) the polyalkyleneimine backbone has a mass average molecular weight M W  of from 600 g/mol to 100 000 g/mol,   (b) the N-hydrogen atoms are each substituted by a polyoxyalkylene group comprising an oxyethylene and a C 3  to C 6  oxyalkylene unit,   (c) the average number of oxyalkylene units in the polyoxyalkylene groups is of from more than 10 to less than 30 per N-hydrogen atom in the polyalkyleneimine, and   
       wherein the alkyleneimine is an ethyleneimine. 
     
     
         2 . The composition according to  claim 1 , wherein the average number of oxyalkylene units in the polyoxyalkylene group is from 11 to 28 per N-hydrogen atom. 
     
     
         3 . The composition according to  claim 1 , wherein the at least one additive is a polyalkyleneimine of formula L1 
       
         
           
           
               
               
           
         
         or derivatives thereof obtainable by protonation or quaternization, wherein
 X L1  is independently selected from the group consisting of ethanediyl; 
 A L1  is a continuation of the polyalkyleneimine backbone by branching; 
 R L1  is a polyoxyalkylene unit of formula —(X L11 O) r (X L12 O) s —R L11 ; 
 R L2  is selected from the group consisting of R L1  and R L3 ; 
 R L3  is selected from the group consisting of C 1  to C 12  alkyl, C 1  to C 12  alkenyl, C 1  to C 12  alkynyl, C 6  to C 20  alkylaryl, C 6  to C 20  arylalkyl, and C 6  to C 20  aryl; 
 X L11  is ethanediyl; 
 X L12  is, for each n, independently selected from the group consisting of a C 3  to C 6  alkanediyl, (2-hydroxymethyl)ethane-1,2-diyl, butane-1,2-diyl, butane-2,3-diyl, 2-methyl-propane-1,2-diyl (isobutylene), pentane-1,2-diyl, pentane-2,3-diyl, 2-methyl-butane-1,2-diyl, 3-methyl-butane-1,2-diyl, hexane-2,3-diyl, hexane-3,4-diyl, 2-methyl-pentane-1,2-diyl, 2-ethylbutane-1,2-diyl, 3-methyl-pentane-1,2-diyl, decane-1,2-diyl, 4-methyl-pentane-1,2-diyl and (2-phenyl)-ethane-1,2-diyl, and mixtures thereof; 
 R L11  is each independently the group consisting of hydrogen, C 1  to C 12  alkyl, C 2  to C 12  alkenyl, C 2  to C 12  alkynyl, C 6  to C 18  arylalkyl, C 5  to C 12  aryl, C 2  to C 12  alkylcarbonyl, and mixtures thereof; 
 s, r are integers selected so that the arithmetic average number of oxyalkylene units in the R L1  groups 1 to n (1/p Σ n=1   n  p) is a number from above 10 to below 30, wherein p is the sum of r and s; and 
 q, n, m, o are integers with the proviso that (q+n+m+o) is from 10 to 24000 and n is 1 or more. 
 
       
     
     
         4 . (canceled) 
     
     
         5 . The composition according to  claim 3 , wherein the relative amount s/(s+r) of the C 3  to C 6  oxyalkylene units in R L1  is from 7% to 50%. 
     
     
         6 . The composition according to  claim 3 , wherein the C 3  to C 6  oxyalkylene is oxypropylene. 
     
     
         7 . The composition according to  claim 3 , wherein p is selected so that the arithmetic average number of oxyalkylene units in the R L1  groups 1 to n (1/n Σ n=1   n  p) is a number from 11-28. 
     
     
         8 . The composition according to  claim 3 , wherein q+n+m+o is from 15 to 10000. 
     
     
         9 . The composition according to  claim 3 , wherein q+n+m+o is from 25 to 65 or from 1000 to 1800. 
     
     
         10 . The composition according to  claim 3 , wherein o is 0. 
     
     
         11 . The composition according to  claim 1 , wherein the average number of oxyalkylene units in the polyoxyalkylene group is from 12 to 25 per N-hydrogen atom. 
     
     
         12 . The composition according to  claim 1 , further comprising one or more accelerating agents, one or more suppressing agents, or a combination thereof. 
     
     
         13 . A method of using the composition according to  claim 1 , the method comprising using the composition for depositing copper on a substrate comprising a recessed feature comprising a conductive feature bottom and a dielectric feature side wall, wherein the recessed feature has an aperture size from 500 nm to 500 μm. 
     
     
         14 . A process for electrodepositing copper on a substrate comprising a recessed feature comprising a conductive feature bottom and a dielectric feature side wall, the process comprising:
 a) contacting a composition according to  claim 1  with the substrate, and   b) applying a current to the substrate for a time sufficient to deposit a copper layer into the recessed feature,   wherein the recessed feature has an aperture size from 500 nm to 500 μm.   
     
     
         15 . The process according to  claim 14 , wherein the aperture size is from 1 μm to 200 μm. 
     
     
         16 . The composition according to  claim 3 , wherein X L12  is propane 1,2 diyl. 
     
     
         17 . The composition according to  claim 3 , wherein p is selected so that the arithmetic average number of oxyalkylene units in the R L1  groups 1 to n (1/n Σ n=1   n  p) is a number from 13 to 25. 
     
     
         18 . The composition according to  claim 3 , wherein q+n+m+o is from 20 to 5000. 
     
     
         19 . The composition according to  claim 1 , wherein the average number of oxyalkylene units in the polyoxyalkylene group is from 13 to 23 per N-hydrogen atom.