Composition for copper bump electrodeposition comprising a leveling agent
Disclosed herein is a composition for copper bump electrodeposition 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 900 g/mol to 100 000 g/mol, (b) the N-hydrogen atoms are each substituted by a C2 to C6 polyoxyalkylene group, and (c) the average number of oxyalkylene units in the polyoxyalkylene group is from more than 10 to less than 30 per N-hydrogen atoms 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 900 g/mol to 100 000 g/mol,
(b) the N-hydrogen atoms are each substituted by a polyoxyalkylene group comprising C 2 to C 6 oxyalkylene units,
(c) the average number of oxyalkylene units in the polyoxyalkylene group 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) p 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 2 to C 12 alkenyl, C 2 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, for each n, independently selected from the group consisting of a C 2 to C 6 alkanediyl, propane-1,2-diyl, (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 selected from 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, sulfate, sulfonate and mixtures thereof;
p is an integer selected so that the arithmetic average number of oxyalkylene units in the R L1 groups 1 to n (1/nΣ n=1 n p) is a number from above 10 to below 30; 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 . The composition according to claim 3 , wherein X L11 is selected from the group consisting of ethanediyl and a combination of ethanediyl and 1,2-propanediyl.
5 . The composition according to claim 3 , wherein R L11 is hydrogen.
6 . 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/nΣ n=1 n p) is a number from 11 to 28.
7 . The composition according to claim 3 , wherein q+n+m+o is from 15 to 10000.
8 . The composition according to claim 3 , wherein q+n+m+o is from 25 to 65 or from 1000 to 1800.
9 . The composition according to claim 3 , wherein o is 0.
10 . 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.
11 . The composition according to claim 1 , further comprising one or more accelerating agents, one or more suppressing agents, or a combination thereof.
12 . 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.
13 . 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.
14 . The process according to claim 13 , wherein the aperture size is from 1 μm to 200 μm.
15 . The composition according to claim 3 , wherein X L11 is ethane 1,2 diyl.
16 . 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/nΣ n=1 n p) is a number from 13 to 25.
17 . The composition according to claim 3 , wherein q+n+m+o is from 20 to 5000.
18 . 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.